CA2205294A1 - Method for producing superheavy oil emulsion fuel and fuel produced thereby - Google Patents
Method for producing superheavy oil emulsion fuel and fuel produced therebyInfo
- Publication number
- CA2205294A1 CA2205294A1 CA002205294A CA2205294A CA2205294A1 CA 2205294 A1 CA2205294 A1 CA 2205294A1 CA 002205294 A CA002205294 A CA 002205294A CA 2205294 A CA2205294 A CA 2205294A CA 2205294 A1 CA2205294 A1 CA 2205294A1
- Authority
- CA
- Canada
- Prior art keywords
- salts
- emulsion fuel
- weight
- oil
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 122
- 239000000446 fuel Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000003381 stabilizer Substances 0.000 claims abstract description 34
- 239000002270 dispersing agent Substances 0.000 claims abstract description 33
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 73
- 239000002245 particle Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 35
- 239000002734 clay mineral Substances 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000011362 coarse particle Substances 0.000 claims description 15
- 239000003945 anionic surfactant Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- -1 residues Substances 0.000 description 124
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 111
- 150000003839 salts Chemical class 0.000 description 68
- 229910052708 sodium Inorganic materials 0.000 description 37
- 239000011734 sodium Substances 0.000 description 37
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 35
- 238000009833 condensation Methods 0.000 description 35
- 230000005494 condensation Effects 0.000 description 35
- 150000003863 ammonium salts Chemical class 0.000 description 34
- 159000000001 potassium salts Chemical class 0.000 description 34
- 159000000000 sodium salts Chemical class 0.000 description 34
- 229910052783 alkali metal Inorganic materials 0.000 description 28
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 18
- 159000000003 magnesium salts Chemical class 0.000 description 18
- 150000007513 acids Chemical class 0.000 description 16
- 159000000007 calcium salts Chemical class 0.000 description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 12
- 150000002169 ethanolamines Chemical class 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 238000013019 agitation Methods 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 11
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 10
- 229920005610 lignin Polymers 0.000 description 10
- 235000019354 vermiculite Nutrition 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 8
- 150000003871 sulfonates Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920001732 Lignosulfonate Polymers 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000332 continued effect Effects 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229920001477 hydrophilic polymer Polymers 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 3
- VOEFELLSAAJCHJ-UHFFFAOYSA-N 1-(3-chlorophenyl)-2-(methylamino)propan-1-one Chemical compound CNC(C)C(=O)C1=CC=CC(Cl)=C1 VOEFELLSAAJCHJ-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229940069096 dodecene Drugs 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- 235000010493 xanthan gum Nutrition 0.000 description 3
- 239000000230 xanthan gum Substances 0.000 description 3
- 229940082509 xanthan gum Drugs 0.000 description 3
- UEJBEYOXRNGPEI-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-(methylamino)propan-1-one Chemical compound CNC(C)C(=O)C1=CC=C(Cl)C=C1 UEJBEYOXRNGPEI-UHFFFAOYSA-N 0.000 description 2
- DOGQRRGVLIGIEG-UHFFFAOYSA-N 1-(prop-2-enoylamino)butane-2-sulfonic acid Chemical compound CCC(S(O)(=O)=O)CNC(=O)C=C DOGQRRGVLIGIEG-UHFFFAOYSA-N 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical class CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000004808 allyl alcohols Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- BOOMOFPAGCSKKE-UHFFFAOYSA-N butane-2-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCC(C)S(O)(=O)=O BOOMOFPAGCSKKE-UHFFFAOYSA-N 0.000 description 2
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 2
- 229910000281 calcium bentonite Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 229960000878 docusate sodium Drugs 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
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- 229910000280 sodium bentonite Inorganic materials 0.000 description 2
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- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
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- 229910052626 biotite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
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- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000010779 crude oil Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- NJGVXNDHVPXKBQ-UHFFFAOYSA-N diazanium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [NH4+].[NH4+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC NJGVXNDHVPXKBQ-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
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- 239000010440 gypsum Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 235000010494 karaya gum Nutrition 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
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- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- 235000010491 tara gum Nutrition 0.000 description 1
- 239000000213 tara gum Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
- C10L2250/06—Particle, bubble or droplet size
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
- C10L2250/08—Emulsion details
- C10L2250/082—Oil in water (o/w) emulsion
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A method for producing a superheavy oil emulsion fuel comprising the steps of (i) preparing a liquid mixture comprising a superheavy oil, water, one or more nonionic surfactants having an HLB (hydrophilic-lipophilic balance) of 13 to 19, and optionally one or more stabilizers, and then agitating the resulting liquid mixture with a high shear rate of 1000/sec to 60000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 74 to 82% by weight; and (ii) adding at least one of ionic dispersants, and optionally water, to the emulsion fuel obtained in step (i), and then blending and agitating the resulting liquid mixture with a shear rate of 10/sec to 10000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 68 to 79% by weight. In step (i), the nonionic surfactants are contained in an amount of from 0.1 to 0.8% by weight of the emulsion fuel obtained in step (i), and the stabilizers are contained in an amount of from 0.001 to 0.5% by weight of the emulsion fuel obtained in step (i). In step (ii), the ionic dispersants are contained in an amount of from 0.01 to 0.5% by weight of the emulsion fuel obtained in step (ii).
Description
CA 0220~294 1997-0~-14 SPECIFICATION
METHOD FOR PRODUCING SUPERHEAVY OIL EMULSION FUEL
AND FUEL PRODUCED THEREBY
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a method for producing an oil-in-water type, superheavy oil emulsion fuel which is usable as fuels for thermoelectric power generation and an emulsion fuel produced by the above method.
Discussion of the Related Art It has been well known that the superheavy oil emulsion fuels give stable emulsion fuels when used together with additives, such as emulsifiers and stabilizers, and various excellent emulsifiers to be used in emulsion fuel compositions have been developed (See Japanese Patent Laid-Open No. 1-185394, USP 5,024,676, and Japanese Patent Laid-Open No. 1-313595). However, insufficient long-term storage stability and requiring large amounts of emulsifiers are being problems in the conventional methods. Also, the concentration of the superheavy oil has been demanded to be made as high as possible. This is owing to the fact that higher the CA 0220~294 1997-0~-14 concentration of the superheavy oil, or lower the concentration of water in the emulsion fuel, smaller the heat loss during the combustion of the emulsion fuel owing to water, so that the resulting emulsion fuel is made more valuable. Therefore, when an emulsion fuel having a high concentration of a superheavy oil and a small amount of coarse particles, with good flowability and easy handling can be prepared, it is highly advantageous in aspects of being able to, as needed, dilute the emulsion fuel as well as having smaller heat loss.
Accordingly, an object of the present invention is to provide a method for producing an easy-to-handle superheavy oil emulsion fuel having a high superheavy oil concentration, good flowability, and good long-term storage stability.
Another object of the present invention is to provide a superheavy oil emulsion fuel obtainable by the above method.
These and other objects of the present invention will be apparent from the following description.
SUMMARY OF THE INVENTION
As a result of intensive research in view of solving the above problems, the present inventors have found that a stable emulsion can be obtained by agitating particular CA 0220~294 1997-0~-14 amounts of a superheavy oil, water, and nonionic surfactants, and optionally stabilizers first under a high shear rate, and then agitating, after adding ionic dispersants, under medium shear rate, to give an emulsion fuel at a desired concentration of the superheavy fuel.
The present invention has been completed based upon these findings. Incidentally, in the second step, only at least one of surfactants and stabilizers may be added without adding water.
Specifically, the present invention is concerned with the following:
(1) A method for producing a superheavy oil emulsion fuel comprising the steps of:
(i) preparing a liquid mixture comprising a superheavy oil, water, one or more nonionic surfactants having an HLB (hydrophilic-lipophilic balance) of 13 to 19, and optionally one or more stabilizers, and then agitating the resulting liquid mixture with a high shear rate of 1000/sec to 60000/sec, to give an oil-in-water (0/W) type emulsion fuel having a superheavy oil concentration of from 74 to 82%
by weight, wherein the nonionic surfactants are contained in an amount of from 0.1 to 0.8% by weight of the emulsion fuel obtained in step CA 0220~294 1997-0~-14 (i), and wherein the stabilizers, when added, are contained in an amount of from 0.001 to 0.5%
by weight of the emulsion fuel obtained in step (i); and (ii) adding at least one of ionic dispersants, and optionally water, to the emulsion fuel obtained in step (i), and then blending and agitating the resulting liquid mixture with a shear rate of 10/sec to 10000/sec, to give an oil-in-water (0/W) type emulsion fuel having a superheavy oil concentration of from 68 to 79% by weight, wherein the ionic dispersants are contained in an amount of from 0.01 to 0.5% by weight of the emulsion fuel obtained in step (ii);
METHOD FOR PRODUCING SUPERHEAVY OIL EMULSION FUEL
AND FUEL PRODUCED THEREBY
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a method for producing an oil-in-water type, superheavy oil emulsion fuel which is usable as fuels for thermoelectric power generation and an emulsion fuel produced by the above method.
Discussion of the Related Art It has been well known that the superheavy oil emulsion fuels give stable emulsion fuels when used together with additives, such as emulsifiers and stabilizers, and various excellent emulsifiers to be used in emulsion fuel compositions have been developed (See Japanese Patent Laid-Open No. 1-185394, USP 5,024,676, and Japanese Patent Laid-Open No. 1-313595). However, insufficient long-term storage stability and requiring large amounts of emulsifiers are being problems in the conventional methods. Also, the concentration of the superheavy oil has been demanded to be made as high as possible. This is owing to the fact that higher the CA 0220~294 1997-0~-14 concentration of the superheavy oil, or lower the concentration of water in the emulsion fuel, smaller the heat loss during the combustion of the emulsion fuel owing to water, so that the resulting emulsion fuel is made more valuable. Therefore, when an emulsion fuel having a high concentration of a superheavy oil and a small amount of coarse particles, with good flowability and easy handling can be prepared, it is highly advantageous in aspects of being able to, as needed, dilute the emulsion fuel as well as having smaller heat loss.
Accordingly, an object of the present invention is to provide a method for producing an easy-to-handle superheavy oil emulsion fuel having a high superheavy oil concentration, good flowability, and good long-term storage stability.
Another object of the present invention is to provide a superheavy oil emulsion fuel obtainable by the above method.
These and other objects of the present invention will be apparent from the following description.
SUMMARY OF THE INVENTION
As a result of intensive research in view of solving the above problems, the present inventors have found that a stable emulsion can be obtained by agitating particular CA 0220~294 1997-0~-14 amounts of a superheavy oil, water, and nonionic surfactants, and optionally stabilizers first under a high shear rate, and then agitating, after adding ionic dispersants, under medium shear rate, to give an emulsion fuel at a desired concentration of the superheavy fuel.
The present invention has been completed based upon these findings. Incidentally, in the second step, only at least one of surfactants and stabilizers may be added without adding water.
Specifically, the present invention is concerned with the following:
(1) A method for producing a superheavy oil emulsion fuel comprising the steps of:
(i) preparing a liquid mixture comprising a superheavy oil, water, one or more nonionic surfactants having an HLB (hydrophilic-lipophilic balance) of 13 to 19, and optionally one or more stabilizers, and then agitating the resulting liquid mixture with a high shear rate of 1000/sec to 60000/sec, to give an oil-in-water (0/W) type emulsion fuel having a superheavy oil concentration of from 74 to 82%
by weight, wherein the nonionic surfactants are contained in an amount of from 0.1 to 0.8% by weight of the emulsion fuel obtained in step CA 0220~294 1997-0~-14 (i), and wherein the stabilizers, when added, are contained in an amount of from 0.001 to 0.5%
by weight of the emulsion fuel obtained in step (i); and (ii) adding at least one of ionic dispersants, and optionally water, to the emulsion fuel obtained in step (i), and then blending and agitating the resulting liquid mixture with a shear rate of 10/sec to 10000/sec, to give an oil-in-water (0/W) type emulsion fuel having a superheavy oil concentration of from 68 to 79% by weight, wherein the ionic dispersants are contained in an amount of from 0.01 to 0.5% by weight of the emulsion fuel obtained in step (ii);
(2) The method described in item (1), wherein at least one of anionic surfactants and cationic surfactants is further added in the preparation of the liquid mixture in step (i), the weight ratio of at least one of anionic surfactants and cationic surfactants to the nonionic surfactants being from 1/100 to 1/4;
(3) The method described in item (1) or item (2), wherein the stabilizers are at least one member selected from polymeric compounds and water-swellable clay minerals;
(4) The method described in any one of items (1) to (3), wherein the oil-in-water (0/W) type emulsion fuel in step CA 0220~294 1997-0~-14 (i) has a superheavy oil concentration of from 77 to 81%
by weight;
by weight;
(5) The method described in any one of items (1) to (4), wherein in the preparation of the liquid mixture in step (i), the nonionic surfactants are contained in an amount of from 0.2 to 0.4% by weight of the emulsion fuel obtained in step (i), and the stabilizers, when added, are contained in an amount of from 0.005 to 0.1% by weight of the emulsion fuel obtained in step (i); and wherein in step (ii), the dispersants are contained in an amount of from 0.02 to 0.2% by weight of the emulsion fuel obtained in step (ii);
(6) The method according to any one of items (1) to (5), wherein the weight ratio of the nonionic surfactants to the ionic dispersants, namely nonionic surfactants/ionic dispersants, is from 90/10 to 60/40 in the superheavy oil emulsion fuel obtained in step (ii);
(7) The method described in any one of items (1) to (6), wherein the liquid mixture in step (i) is agitated with a shear rate of from 5000/sec to 20000/sec, and wherein the liquid mixture in step (ii) is agitated with a shear rate of from 100/sec to 6000/sec;
(8) The method described in any one of items (1) to (7), wherein the oil-in-water (0/W) type emulsion fuel obtained in step (i) comprises oil droplets having a particle size CA 0220~294 1997-0~-14 distribution of which a 50%-cumulative particle size is from 3 to 30 ,um, and coarse particles having particle sizes of 150 ,um or more occupy 3% by weight or less in the entire oil droplets;
(9) The method described in any one of items (1) to (8), wherein the oil-in-water (0/W) type emulsion fuel obtained in step (i) has a viscosity at 25~C of from 400 to 3000 c.p.;
(10) The method described in any one of items (1) to (9), wherein a homomixer equipped with a high-shear turbine mixer is used in step (i) as an agitator with a high shear rate;
(11) The method described in any one of items (1) to (10), wherein the oil-in-water (0/W) type emulsion fuel obtained in step (i) comprises oil droplets of which coarse particles having particle sizes of 150 ,um or more occupy 2% by weight or less in the entire oil droplets;
(12) The method described in any one of items (1) to (11), wherein in the preparation of the liquid mixture in step (i), at least one member selected from magnesium acetate, magnesium sulfate, magnesium nitrate, calcium acetate, calcium sulfate, calcium nitrate, iron acetate, iron sulfate, and iron nitrate is further added to the liquid mixture, in an amount of from 0.01 to 0.2% by weight of the emulsion fuel obtained in step (i); and CA 0220~294 1997-0~-14 (13) A superheavy oil emulsion fuel obtainable by the method described in any one of items (1) to (12).
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be explained in detail below.
The method for producing superheavy oil emulsion fuel of the present invention comprises two steps, namely step (i) and step (ii). The method of the present invention will be described in detail for each step (i) and step ( ii ) .
1. Step (i) Step (i) comprises preparing a liquid mixture comprising a superheavy oil, water, one or more nonionic surfactants having an HLB (hydrophilic-lipophilic balance) of 13 to 19, and optionally one or more stabilizers, and then agitating the resulting liquid mixture with a high shear rate of 1000/sec to 60000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 74 to 82~ by weight, wherein the nonionic surfactants are contained in an amount of from 0.1 to 0.8~ by weight of the emulsion fuel obtained in step (i), and wherein the stabilizers, when added, are contained in an amount of from 0.001 to 0.5~ by weight of CA 0220~294 1997-0~-14 the emulsion fuel obtained in step (i).
The "superheavy oil" usable in the present invention refers to those in a solid or semi-fluid state at room temperature, which do not flow unless heated to a high temperature. Examples of the superheavy oils include the following:
(1) Petroleum asphalts and mixtures thereof;
(2) Various treated products of petroleum asphalts, intermediates, residues, and mixtures thereof.
(3) High pour point-oils which do not even flow at high temperatures, or crude oils;
(4) Petroleum tar pitches and mixtures thereof; and (5) Bitumens (Orinoco tar and athabasca bitumen).
Examples of the nonionic surfactants usable in the present invention include the following ones:
(i) Alkylene oxide adducts of compounds having phenolic hydroxyl groups, such as phenol, m-cresol, butylphenol, octylphenol, nonylphenol, dodecylphenol, p-cumylphenol, and bisphenol A.
(ii) Alkylene oxide adducts of formalin (formaldehyde) condensates of compounds having phenolic hydroxyl groups, such as alkylphenols, phenol, m-cresol, styrenated phenol, and benzylated phenol, wherein the average degree of condensation is 1.2 to 100, preferably 2 to 20.
CA 0220~294 1997-0~-14 (iii)Alkylene oxide adducts of aliphatic alcohols and/or aliphatic amines each having 2 to 50 carbon atoms.
(iv) Block or random addition polymers of ethylene oxide/propylene oxide, ethylene oxide/butylene oxide, ethylene oxide/styrene oxide, ethylene oxide/propylene oxide/butylene oxide, ethylene oxide/propylene oxide/ethylene oxide, and ethylene oxide/propylene oxide/styrene oxide.
(v) Alkylene oxide adducts of polyhydric alcohols, such as glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerols, ethylene glycol, polyethylene glycols, propylene glycol, and polypropylene glycols, or those of esters formed between the above-described polyhydric alcohols and fatty acids having 8 to 18 carbon atoms.
(vi) Alkylene oxide adducts of polyvalent amines having a plurality of active hydrogen atoms, such as ethylenediamine, tetraethylenediamine, and polyethyleneimine (weight-average molecular weight:
600 to 10,000).
(vii)Products formed by addition reaction of alkylene oxides with a mixture comprising one mol of fats and oils comprising triglyceride and 0.1 to 5 mol of one or more polyhydric alcohols and/or water, the CA 0220~294 1997-0~-14 polyhydric alcohol being at least one member selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylene glycol, polyethylene glycols having a weight-average molecular weight of 1000 or less, propylene glycol, and polypropylene glycols having a weight-average molecular weight of 1000 or less.
In each of the nonionic surfactants (i) to (vii), the alkylene oxide means, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and combinations thereof.
In the present invention, the nonionic surfactants may be used alone or in combination of two or more kinds.
Among the above nonionic surfactants, a preference is given those listed under item (i), specifically, alkylene oxide adducts of compounds having phenolic hydroxyl groups, such as octylphenol, nonylphenol, and dodecylphenol.
The nonionic surfactants usable in the present invention have an HLB of usually from 13 to 19, preferably from 13.5 to 15.5. The HLB of the nonionic surfactants is from 13 to 19 in order to obtain stable emulsion. The "HLB" values in the present invention refer to an abbreviation of a hydrophilic-lipophilic balance calculated from the Griffin's equation. Specifically, the CA 0220~294 1997-0~-14 HLB is an index for surface activity by expressing intensity ratios between a hydrophilic property and a lipophilic property of amphiphilics. Here, the found values of Griffin et al. are employed (W.C. Griffin, "Kirk-Othmer Encyclopedia of Chemical Technology," 3rd Ed., Vol. 8, p.913-916, John-Wiley (1979)).
The nonionic surfactant in the present invention used is contained in an amount of from 0.1 to 0.8% by weight, preferably from 0.2 to 0.4% by weight, of the emulsion fuel obtained in step (i). The amount is preferably 0.8%
by weight or less, from the aspect of maintaining good particle size of the oil particles in the resulting emulsion fuel without being too small, and the amount is preferably 0.1% by weight or more, from the aspect of maintaining good particle size of the oil particles without being too large as well as having good emulsion stability by the sufficient inclusion of the surfactants.
In the preparation of the liquid mixture in step (i), in addition to the nonionic surfactants, commercially available anionic surfactants and cationic surfactants may be optionally added to the liquid mixture, a weight ratio of the optional surfactants to the nonionic surfactant being preferably from 1/100 to 1/4, more preferably from 1/20 to 1/5.
Examples of the anionic surfactants usable in the CA 0220~294 1997-0~-14 present invention include the following ones.
(i) Sulfonates of aromatic ring compounds, such as naphthalenesulfonates, alkylnaphthalenesulfonates, alkylphenolsulfonates, and alkylbenzenesulfonates, or formalin (formaldehyde) condensates of sulfonates of aromatic ring compounds, wherein the average degree of condensation of formalin is from 1.2 to 100, more preferably from 2 to 20, and wherein the sulfonates are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(ii) Lignin sulfonic acid, salts thereof, or derivatives thereof, formalin (formaldehyde) condensates of lignin sulfonic acid and sulfonic acids of aromatic compounds, such as naphthalenesulfonic acid and alkylnaphthalenesulfonic acids, and salts thereof, wherein the salts for both the lignin sulfonates and the sulfonates of aromatic compounds are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or CA 0220~294 1997-0~-14 alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts, and wherein the average degree of condensation of formalin is from 1.2 to 50, preferably from 2 to 20.
Among the lignins, excellent performance at high temperatures can be particularly achieved when a modified lignin, for instance, those substituted by one or more carboxyl groups, is used.
(iii)Polystyrenesulfonic acids or salts thereof, copolymers of styrenesulfonic acid with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified hy ammonium salts;
lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Here, typical examples of the copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, acrylic ester, olefins, allyl alcohols and ethylene oxide adducts thereof, and acrylamide methylpropylsulfonic acid.
(iv) Polymers of dicyclopentadienesulfonic acid or CA 0220~294 l997-0~-l4 salts thereof, wherein the weight-average molecular weight of the polymers is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(v) Copolymers of maleic anhydride and/or itaconic anhydride with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 1,500 to 100,000, and wherein the salts are exemplified by ammonium salts; and alkali metal salts, such as sodium salts and potassium salts. Here, typical examples of the copolymerizable monomers include olefins, such as ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and hexadecene, styrene, vinyl acetate, acrylic ester, acrylic acid, and methacrylic acid.
(vi) Maleinized liquid polybutadienes or salts thereof, wherein the weight-average molecular weight of the liquid polybutadienes as the starting CA 0220~294 l997-0~-l4 materials is from 500 to 200,000, preferably from 1,000 to 50,000, and wherein the degree of maleinization is at a level necessary for dissolving the maleinized liquid polybutadiene in water, preferably from 40 to 70%, and wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(vii)Anionic surfactants having in the molecule one or two hydrophilic groups, selected from the following (a) to (h):
(a) Sulfuric ester salts of alcohols having 4 to 18 carbon atoms, wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecyl sulfate and sodium octyl sulfate.
(b) Alkanesulfonic acids, alkenesulfonic acids, and/or alkylarylsulfonic acids, each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, CA 0220~294 l997-0~-l4 diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecylbenzene sulfonate, sodium butylnaphthalene sulfonate, and sodium dodecane sulfonate.
(c) Sulfates or phosphates of alkylene oxide adducts of compounds having in the molecule one or more active hydrogen atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Typical examples thereof include sulfuric ester sodium salts of polyoxyethylene(3 mol) nonyl phenyl ether, and phosphoric ester sodium salts of polyoxyethylene(3 mol) dodecyl ether.
(d) Sulfosuccinic ester salts of saturated or unsaturated fatty acids having 4 to 22 carbon atoms, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Typical examples thereof include sodium CA 0220~294 1997-0~-14 dioctylsulfosuccinate, ammonium dioctylsulfosuccinate, and sodium dibutylsulfosuccinate.
(e) Alkyldiphenylether disulfonic acids or salts thereof, of which the alkyl group has 8 to 18 carbon atoms, and wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(f) Rosins or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Examples thereof include mixed tall acids comprising a tall rosin and a higher fatty acid, and salts thereof.
(g) Alkanefatty acids or alkenefatty acids each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(h) a-Sulfofatty ester salts of which the alkyl group has 4 to 22 carbon atoms and derivatives thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or CA 0220~294 1997-0~-14 alkaline earth metal salts, such as sodium salts, potassium salts, and magnesium salts.
Among the anionic surfactants listed above, a preference is given to the lignin sulfonates, the formalin condensates of lignin sulfonic acid and the formalin condensates of naphthalenesulfonic acid or salts thereof, and the formalin condensates of naphthalenesulfonates because they show overall superior performance in charging the particles.
The cationic surfactants usable in the present invention are the following ones.
(i) Alkylamine salts and/or alkenylamine salts obtainable by neutralizing an alkylamine or alkenylamine, each of alkyl or alkenyl group having 4 to 18 carbon atoms, with an inorganic acid and/or an organic acid, such as hydrochloric acid and acetic acid.
(ii) Quaternary ammonium salts represented by the following general formulae (A), (B), and (C):
R2 ' ~
R,-- I -- R 4 X- (A) wherein R1, R2, R3, and R4, which may be identical or different, independently stand for an alkyl group or CA 0220~294 1997-0~-14 alkenyl group, each having 1 to 18 carbon atoms; and X~ stands for a counter anion, including chlorine ion or bromine ion;
R2 ' +
R, -N -- R3 X- (B) [~
wherein R1, R2, R3, and X~ are as defined above; and +
X- (C) wherein Rs stands for an alkyl group or alkenyl group having 8 to 18 carbon atoms; R6 stands for a hydrogen atom or a methyl group; and X~ is as defined above.
(iii)Alkylbetaines or alkenylbetaines represented by the following general formula:
,CH3 R- +N- CH3 \CH2 C00-wherein R stands for an alkyl group or alkenyl group, 2 5 each having 8 to 18 carbon atoms.
CA 0220~294 1997-0~-14 (iv) Alkylamine oxides or alkenylamine oxides represented by the following general formula:
R--N ~ 0 wherein R is as defined in item (iii).
(v) Alkylalanines or alkenylalanines represented by the following general formula:
R- +NlCH2 CH2 C00-\C H3 wherein R is as defined in item (iii).
(vi) Alkylene oxide adduct polymers of diamine or triamine represented by the following general formula (D) or (E):
RNH C 3 H6 NHY (D) y RNHC3 H6 N < (E) y wherein R is as defined in item (iii); and Y and Y', which may be identical or different, each stands for an oxyethylene moiety represented by the general CA 0220~294 1997-0~-14 formula:
i C2 H4 O) m H
wherein m stands for a number of from 1 to 50.
(vii)Polyamine salts represented by the following formula (F) or (G):
RNHC3 H6 NHX' (F) RNH (C3 H6 NH)2X' (G) wherein R is as defined in item (iii); and X' stands for an inorganic acid or organic acid, such as hydrochloric acid and acetic acid.
Examples of stabilizers which may be used in combination with the nonionic surfactants in step (i) include (l) polymeric compounds, including naturally occurring polymers and synthetic polymers, and (2) water-swellable clay minerals. In other words, the stabilizers usable in the present invention may be selected from items (1) and (2) listed below.
(1) Polymeric Compounds Hydrophilic Naturally Occurrinq Polymers Derived from Naturally Occurrinq Substances CA 0220~294 1997-0~-14 -- Hydrophilic Polymers Derived from Microorganism (Polysaccharides) 1) Xanthan gum 2 ) Pullulan 3) Dextran -- Hydrophilic Polymers Derived from Plants (Polysaccharides) 1) Derived from marine algae: agar, carrageenan, furcellaran, alginic acid and salts (Na, K, NH4, Ca, or Mg) thereof 2) Derived from seeds: locust bean gum, guar gum, tara gum 3) Trees (exudates): gum arabic, gum karaya, gum tragacanth; and 4) Derived from fruits: pectin -- Hydrophilic Polymers Derived from Animals (Proteins) 1) Gelatin 2) Casein -- Naturally Occurring Polymer Derivatives 1) Cellulose derivatives, such as carboxymethylcellulose 2) Chemically modified starch Water-Soluble Synthetic Polymers CA 0220~294 1997-0~-14 (a) Homopolymers or copolymers of acrylic acidor derivatives thereof represented by the following general formula:
~ R' CH2 -C Z, ) C O2 Ml /n wherein R' stands for a hydrogen atom, a methyl group, or an ethyl group; M1 stands for a hydrogen atom, a sodium ion, a potassium ion, a lithium ion, or an ammonium ion; Z1 stands for a divalent group which is derived from a monomer and salts thereof copolymerizable therewith, the divalent group being represented by the following general formula:
CO2 M, wherein R' and M1 are as defined above, wherein the salts of the copolymerizable monomers are exemplified by ammonium salts, sodium salts, potassium salts, and lithium salts; and n stands for a number of from 50 to CA 0220~294 1997-0~-14 100,000. Examples of the copolymerizable monomers include maleic acid (anhydride), itaconic acid (anhydride), a-olefins, acrylamide, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, and acrylamidomethylpropylsulfonic acid, and salts thereof, including ammonium salts, sodium salts, potassium salts, and lithium salts; dialkyl aminoethyl methacrylates, such as dimethyl aminoethyl methacrylate and diethyl aminoethyl methacrylate and salts thereof, including halogenides, such as chloride, diethyl sulfate, and dimethyl sulfate.
(b) Homopolymers or copolymers of acrylamide or derivatives thereof represented by the following general formula:
CH2 -CH-Z2 ) n Cl O
NH
R~
wherein R" stands for a hydrogen atom or a C2H40H
group; Z2 stands for a divalent group which is derived from a monomer or salts thereof, the divalent group being represented by the CA 0220~294 1997-0~-14 following general formula:
Cl O
NH
R
wherein R" is as defined above, and wherein the salts of the copolymerizable monomers are exemplified by ammonium salts, sodium salts, potassium salts, and lithium salts; and n stands for a number of from 50 to 100,000. Examples of the copolymerizable monomers include vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, acrylamidomethylpropylsulfonic acid, and salts thereof, including ammonium salts, sodium salts, potassium salts, and lithium salts; dialkyl aminoethyl methacrylates, such as dimethyl aminoethyl methacrylate and dimethyl aminoethyl methacrylate and salts thereof, quaternary compounds thereof, including halogenides, such as chloride, diethyl sulfate, and dimethyl sulfate; styrene; a-olefins having 2 to 18 carbon atoms; and vinylallyl alcohols.
( C ) Homopolymers of maleic anhydride or CA 0220~i294 1997~0~i~14 -- 26 ~
itaconic anhydride, or copolymers thereof represented by the following general formula:
( M2-- Z3 ) n wherein M2 stands for a maleic anhydride unit or itaconic anhydride unit; Z3 stands for an a-olefin unit, the a-olefins including ethylene, propylene, butylene, isobutylene, octene, decene, and dodecene, or a styrene unit; and n stands for a number of from 50 to 100,000.
(d) Polyvinyl alcohols or copolymers thereof represented by the following general formula:
~CH2 --CH -- Z~
~ OH Jn wherein Z4 stands for a vinyl acetate unit or styrene unit; and n' stands for a number of from 30 to 100,000.
( e) Homopolymers of vinylpyrrolidone, or copolymers thereof represented by the following general formula:
CA 0220~294 1997-0~-14 CH2 -Cl H Z6) N O n / \~
wherein Zs stands for a divalent group which is derived from a monomer copolymerizable with a vinylpyrrolidone monomer, wherein the salts of the monomers copolymerizable with vinylpyrrolidone monomers include ammonium salts, sodium salts, potassium salts, and lithium salts. Examples of the monomers copolymerizable with the vinylpyrrolidone monomer or salts thereof include acrylamide, vinylsulfonic acid, methallylsulfonic acid, maleic anhydride, itaconic anhydride, and salts thereof, such as ammonium salts, sodium salts, potassium salts, and lithium salts; styrene;
~-olefins having 2 to 18 carbon atoms; and n stands for a number of from 50 to 100,000.
(f) Polyalkylene oxides having a weight-average molecular weight of from 10,000 to 5,000,000, wherein the ethylene oxide content is 95~ by weight or more, which may include those containing in the molecule 5~ by weight or less CA 0220~294 1997-0~-14 of various block polymers of propylene oxide, butylene oxide, and styrene oxide or alkylallyl groups or alkyl groups.
Among these polymeric compounds, naturally occurring polymeric derivatives, including cellulose derivatives, such as carboxymethylcellulose, and hydrophilic polymers derived from microorganism, such as xanthan gum, are suitably used in the present invention.
(2) Water-Swellable Clay Minerals The water-swellable clay minerals usable in the present invention include the following ones.
The clay minerals usable in the present invention is a highly swellable fine clay mineral, wherein the term "highly swellable" clay minerals refer to those bound with a large amount of water molecules when the clay minerals are suspended in water, so as to have a relaxation time (T2) for water molecules of preferably from 900 msec or less, more preferably 500 msec or less, the relaxation time for water molecules being measured by a nuclear magnetic resonance spectrometer when the clay minerals are suspended in water in an amount of 1% by weight on a dry basis. When the relaxation time for the water molecules is 900 msec or less, a good binding force of the clay minerals to the water molecules can be maintained, thereby CA 0220~294 1997-0~-14 making it possible to sufficiently attain the effects of the present invention. In addition, the term "fine clay mineral" refers to the clay minerals having an average particle size of preferably from 100 ,um or less. The clay 5 mineral has an average particle size of preferably 100 ,um or less, a good binding force of the clay minerals to the water molecules can be maintained, and at the same time sedimentation of the clay minerals is liable to be inhibited, thereby making it possible to sufficiently attain the effects of the present invention.
Specifically, the fine clay minerals having a high swellability and a high binding force to the water molecules, including smectites, vermiculites, and chlorites, fall within the scope of the present invention.
Among them, however, those having a T2 value exceeding 900 msec are outside the scope of the present invention.
Further, since kaolin produced in Georgia, U.S.A., general kaolin and talc have weak binding forces to the water molecules, they are excluded from the scope of the present 20 invention.
The highly swellable fine clay minerals, such as smectites, vermiculites, and chlorites, usable in the present invention will be explained in detail below.
(A) Smectite has a complicated chemical composition 25 comprising two tetrahedral sheets and one octahedral sheet CA 0220~294 1997-0~-14 inserted therebetween (namely a 2:1 layer), because substitution takes place in a wide range and various ions accompanied by water molecules are intercalated. The smectite is represented by, for example, the following general formula:
Xm(Y ,Y )23Z401o(0H)2 ~ nH20, wherein X stands for K, Na, 1/2Ca, or 1/2Mg; y2+ stands for Mg2+, Fe2+, Mn2+, Ni2+, Zn2+, or Li, Y3+ stands for Al3+, Fe3+, Mn3+, or Cr3+; and Z stands for Si and/or Al, with proviso that X, Y, and Z stand for an intercalated cation, an octahedral cation, and a tetrahedral cation, respectively.
Typical examples of the smectites are the following ones:
Dioctahedral (octahedral cations being mainly trivalent):
Montmorillonites represented by, for example, the following formula:
xo33(All67Mgo33)si4olo(OH)2 ~ nH20;
Beidellites represented by, for example, the following formula:
X033( Al2 ) ( Alo 33Si3 67 ) ~10 ( OH)2 ~ nH20; and Nontronites represented by, for example, the following formula:
XO33(Fe(III)2)(Alo33si3 67)~lO(OH )2 ~ nH2~' 25 Trioctahedral (octahedral cations being mainly divalent):
CA 0220~294 l997-0~-l4 Saponites represented by, for example, the following formula:
XO33(Mg3)( Alo 33si3.67)~10(OH)2 ~ nH20;
Iron saponites represented by, for example, the following formula:
XO33(Mg,Fe(II))3(Alo33si367)olo(oH)z nH20;
Hectorites represented by, for example, the following formula:
Xo.33(Mg267Lio33)Si4010(OH)2 ~ nH20;
Sauconites represented by, for example, the following formula:
Xo33(Mg~Zn)3(si367Al033)~lO(OH)2 ~ nH20; and Stevensites represented by, for example, the following formula:
XO.33/2(Mg297)s i4Ol0 ( OH)2 ~ nH20.
Among the smectites listed above, the montmorillonites, the beidellites, and the nontronites constitute a series which can be subjected to isomorphous substitution. The stevensites have layer charges of one-half of that of the other smectites, and thus having an intermediary property of the dioctahedral smectites and the trioctahedral smectites.
(B) Vermiculites pertain to 2:1 layer silicates and are represented by, for example, the following formula:
(Mg~Fe(III)~Al)23(si4xAlx)olo(oH)2(M~M2 1/2)X ~ nH2~' CA 0220~294 1997-0~-14 In the above formula, M stands for an intercalated exchangeable cation, and when the vermiculite is in the form of coarse particles, M is mainly composed of Mg. "n"
in the above formula stands for the amount of water, and when the intercalated cation is Mg, water forms a bimolecular layer over a wide temperature range and n is in the range of from about 3.5 to 5. "x" in the above formula stands for layer charges which are in the range of from 0.6 to 0.9.
In the above formula, it is assumed that all of the layer charges are generated by the substitution of tetrahedral cations. However, in certain cases, the octahedral sheet may actually carry a negative charge to which the layer charges are ascribed. The number of octahedral cations is 2 to 3, and the vermiculites are classified into dioctahedral vermiculites and trioctahedral vermiculites. The vermiculites in the form of coarse particles obtainable by the weathering of biotite and phlogopite are trioctahedral vermiculites.
(C) The structures of the chlorites are similar to those of the smectites and the vermiculites, and the base plane interval is 14 to 15~. The chlorites are typically a 2:1 hydrated silicate which can be classified into trioctahedral chlorites and dioctahedral chlorites depending on the properties of the 2:1 layer.
CA 0220~294 1997-0~-14 The trioctahedral chlorites are represented by, for example, the following formula:
(R6-x Rx )(si4-xAlx)~lO(OH) 8 .
In the above formula, R2+ is mainly composed of Mg2+
and Fe2+, which may also include Mn2+ and Ni2+; and R3+ is mainly composed of Al, which may also include Fe3+ and Cr3+. "x" in the above formula is a value of from 0.8 to 1.6.
A chlorite wherein R2+ is mainly composed of Mg2+ is so-called "clinochlore" [e.g. (MgsAl)(Si3Al)~10(OH )8]; and a chlorite wherein R2+ is mainly composed of Fe(II) is so-called "chamosite" [e.g. (FesAl)(Si3Al)~10(OH )8]
Examples of other trioctahedral chlorites include "pennantite" wherein R2+ is mainly composed of Mn(II); and "nimite" wherein R2+ is mainly composed of Ni(II).
The dioctahedral chlorites wherein the octahedral cation is mainly composed of Al are classified into the following three kinds.
Sudoite [e.g. (Mg,Al)465(si,Al)4~l0(oH)8;
Cookeite [e.g. (LiAl4)(Si3Al)~10(OH) 8; and Donbassite [e.g. Al442Ro2(si,Al)4~lO(oH)8 The clay minerals comprising montmorillonite, the clay mineral pertaining to smectite, as the main component, and further containing as impurities, quartz, a-cristobalite, opal, feldspar, mica, zeolite, calcite, CA 0220~294 1997-0~-14 dolomite, gypsum, and iron oxide are so-called "bentonite." The bentonites include sodium bentonite rich in Na ions and calcium bentonite rich in Ca ions. Since sodium bentonite has high swellability, it falls within the scope of the clay minerals of the present invention, while calcium bentonite has notably low swellability that it is excluded from the scope of the present invention.
These stabilizers are contained in an amount of from 0.001 to 0.5% by weight, preferably from 0.001 to 0.1% by weight, most preferably from 0.005 to 0.1% by weight, of the emulsion fuel obtained in step (i). The addition of the stabilizers allows to suppress the mobility in the interface of the oil droplets, so that the resulting emulsion fuels may be stabilized.
In addition, aside from the stabilizers mentioned above, at least one member selected from magnesium acetate, magnesium sulfate, magnesium nitrate, calcium acetate, calcium sulfate, calcium nitrate, iron acetate, iron sulfate, and iron nitrate is further added to the liquid mixture, may be added, to thereby give a good emulsion stability effect. In this case, these stabilizers are contained in an amount of from 0.01 to 0.2~ by weight, preferably from 0.05 to 0.1% by weight, of the emulsion fuel obtained in step (i).
In step (i), the agitators to be used when preparing a liquid mixture comprising a superheavy oil, water, a CA 0220~294 1997-0~-14 nonionic surfactant, and optional stabilizers are not particularly required to have high shear rates, and any one of general agitators, such as propeller agitators, will suffice. The agitation after the preparation of the liquid mixture needs to be carried out by agitators with high shear rates. Examples thereof include line mixers, arrow blade turbine blade mixers, full margin-type blade mixers, high-shear turbine mixers, and homogenizers. From the viewpoint of industrial efficiency, homomixers equipped with high-shear turbine mixers are preferably used. Here, the term "high shear rate" refers to a shear rate of from l,000/sec to 60,000/sec, preferably from 5,000/sec to 20, 000/sec. By agitating with such a high shear rate, the oil-in-water (0/W) type emulsion fuel having a concentration of the superheavy oil of from 74 to 82~ by weight, preferably from 77 to 81~ by weight. By agitating the liquid mixture with such a high shear rate, the oil-in water (0/W) emulsion fuel having a superheavy oil concentration of from 74 to 82% by weight, preferably 20 from 77 to 81~ by weight can be produced. The water is added in step (i) so as to make up 100~ by weight with the entire emulsion fuel, namely, the amount of water is from 17 to 25~ by weight.
The kinds and the amounts of the nonionic 25 surfactants, the shear rates, and time required for agitation of the liquid mixture, and viscosity during CA 0220~294 1997-0~-14 agitation have to suitably adjusted so that the oil-in-water (0/W) emulsion fuel obtained in step (i) has a particle size distribution wherein a 50%-cumulative particle size is preferably from 3 to 30 ,um, more preferably 8 to 20 ,um, and wherein coarse particles having particle sizes of 150 ,um or more occupy preferably 3~ by weight or less, more preferably 2% by weight or less, still more preferably 1~ by weight or less, in the entire emulsion fuel. The viscosity of the resulting oil-in-water emulsion fuel is preferably 400 c.p. or more (at 25~C), more preferably from 400 to 3000 C.p. (at 25~C). Incidentally, the term "particle size" used herein refers to particle diameter. The "particle size" and "amount of coarse particles" are evaluated by methods described in Examples which are set forth hereinbelow.
2. Step (ii) Step (ii) comprises adding at least one of water and ionic dispersants to the emulsion fuel obtained in step (i), and then blending and agitating the resulting liquid mixture with a shear rate of 10/sec to 10000/sec, to give an oil-in-water (0/W) type emulsion fuel having a superheavy oil concentration of from 68 to 79% by weight, wherein the ionic dispersants, when added, are contained in an amount of from 0.01 to 0.5% by weight of the emulsion fuel obtained in step (ii).
CA 0220~294 1997-0~-14 The ionic dispersants usable in step (ii) include the following anionic surfactants.
(i) Sulfonates of aromatic ring compounds, such as naphthalenesulfonates, alkylnaphthalenesulfonates, alkylphenolsulfonates, and alkylbenzenesulfonates, or formalin (formaldehyde) condensates of sulfonates of aromatic ring compounds, wherein the average degree of condensation of formalin is from 1.2 to lO0, more preferably from 2 to 20, and wherein the sulfonates are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(ii) Lignin sulfonic acid, salts thereof, or derivatives thereof, formalin (formaldehyde) condensates of lignin sulfonic acid and sulfonic acids of aromatic compounds, such as naphthalenesulfonic acid and alkylnaphthalenesulfonic acids, and salts thereof, wherein the salts for both the lignin sulfonates and the sulfonates of aromatic compounds are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and CA 0220~294 1997-0~-14 triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts, and wherein the average degree of condensation of formalin is from 1.2 to 50, preferably from 2 to 20.
Among the lignins, excellent performance at high temperatures can be particularly achieved when a modified lignin, for instance, those substituted by one or more carboxyl groups, is used.
(iii)Polystyrenesulfonic acids or salts thereof, copolymers of styrenesulfonic acid with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified by ammonium salts;
lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Here, typical examples of the copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, acrylic ester, olefins, allyl alcohols and ethylene oxide adducts thereof, and acrylamide methylpropylsulfonic acid.
CA 0220~294 1997-0~-14 (iv) Polymers of dicyclopentadienesulfonic acid or salts thereof, wherein the weight-average molecular weight of the polymers is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(v) Copolymers of maleic anhydride and/or itaconic anhydride with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 1,500 to 100,000, and wherein the salts are exemplified by ammonium salts; and alkali metal salts, such as sodium salts and potassium salts. Here, typical examples of the copolymerizable monomers include olefins, such as ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and hexadecene, styrene, vinyl acetate, acrylic ester, acrylic acid, and methacrylic acid.
(vi) Maleinized liquid polybutadienes or salts thereof, wherein the weight-average molecular weight CA 0220~294 1997-0~-14 of the liquid polybutadienes as the starting mate-rials is from 500 to 200,000, preferably from 1,000 to 50,000, and wherein the degree of maleinization is at a level necessary for dissolving the maleinized liquid polybutadiene in water, preferably from 40 to 70%, and wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(vii)Anionic surfactants having in the molecule one or two hydrophilic groups, selected from the following (a) to (h):
(a) Sulfuric ester salts of alcohols having 4 to 18 carbon atoms, wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecyl sulfate and sodium octyl sulfate.
(b) Alkanesulfonic acids, alkenesulfonic acids, and/or alkylarylsulfonic acids, each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts; lower CA 0220~294 l997-0~-l4 amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecylbenzene sulfonate, sodium butylnaphthalene sulfonate, and sodium dodecane sulfonate.
(c) Sulfates or phosphates of alkylene oxide adducts of compounds having in the molecule one or more active hydrogen atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Typical examples thereof include sulfuric ester sodium salts of polyoxyethylene(3 mol) nonyl phenyl ether, and phosphoric ester sodium salts of polyoxyethylene(3 mol) dodecyl ether.
(d) Sulfosuccinic ester salts of saturated or unsaturated fatty acids having 4 to 22 carbon atoms, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Typical examples thereof include sodium dioctylsulfosuccinate, ammonium CA 0220~294 1997-0~-14 dioctylsulfosuccinate, and sodium dibutylsulfosuccinate.
(e) Alkyldiphenylether disulfonic acids or salts thereof, of which the alkyl group has 8 to 18 carbon atoms, and wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(f) Rosins or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Examples thereof include mixed tall acids comprising a tall rosin and a higher fatty acid, and salts thereof.
(g) Alkanefatty acids or alkenefatty acids each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(h) a-Sulfofatty ester salts of which the alkyl group has 4 to 22 carbon atoms and derivatives thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, and magnesium salts.
Among the anionic surfactants listed above, a CA 0220~294 1997-0~-14 preference is given to the lignin sulfonates, the formalin condensates of lignin sulfonic acid and the formalin condensates of naphthalenesulfonic acid or salts thereof, and the formalin condensates of naphthalenesulfonates because they show overall superior performance in charging the particles.
The weight ratio of the ionic dispersants to the nonionic surfactants used in step (i) is preferably from 10/90 to 40/60 in the superheavy oil emulsion fuel obtained in step (ii).
The amount of the ionic dispersants in the present invention are so adjusted that the amount thereof makes up from 0.01 to 0.5% by weight, preferably 0.02 to 0.2% by weight of the emulsion fuel obtained in step (ii). The ionic dispersant may be added as it is, or as an aqueous solution.
In addition, cationic surfactants, nonionic surfactants, thickening agents, and the stabilizers, namely polymeric compounds or water-swellable clay minerals usable in step (i), may be added as long as added in an amount expressed by weight ratio to the anionic dispersants, is preferably within the range of from 1/100 to 1/5.
In step (ii), the agitation while adding to and blending at least one of water and ionic dispersants with the emulsion fuel obtained in step (i) is carried out with a generally employed agitator, such as propeller CA 0220~294 1997-0~-14 agitators. In step (ii), subsequent to the preparation of the liquid mixture, the resulting liquid mixture is agitated with a sheer rate of from 10/sec to 10000/sec, preferably from 100/sec to 6000/sec. The shear rate is preferably 10000/sec or less from the viewpoint of significantly reducing the effects to the oil droplet particles of the emulsion fuel obtained in step (ii), thereby making it possible to maintain good long-term storage stability of the resulting emulsion fuel.
10The resulting emulsion fuel obtained in step (ii) comprising the oil-in-water (0/W) droplets has a superheavy oil concentration of from 68 to 79% by weight, preferably from 75 to 79% by weight, and a viscosity at 25~C is preferably from 200 to 1500 c.p., more preferably 15from 300 to 600 c.p. When optionally using water, the concentration of the superheavy oil in the emulsion fuel obtainable in step (ii) is lowered from that in the emulsion fuel obtainable in step (i) preferably by 1 to 6%
by weight. Also, the emulsion fuel obtained in step (ii) comprises the oil-in-water (0/W) droplets having a particle size distribution of which a 50%-cumulative particle size is preferably from 8 to 30 ,um, more preferably from 10 to 20 ,um, still more preferably from 12 to 16 ,um, and coarse particles having particle sizes of 150 ,um or more occupy preferably 3% by weight or less, CA 0220~294 1997-0~-14 more preferably 2~ by weight or less, still more preferably 1~ by weight or less, in the entire oil droplets, which is usable as fuels for thermoelectric power generation.
The superheavy oil emulsion fuel obtainable by the method of the present invention having a high superheavy oil concentration has a small amount of coarse particles and good flowability, and also has good long-term storage stability, so that its handling is made easy, thereby making it highly valuable when used as fuels.
EXAMPLES
The present invention will be explained in detail by means of the following working examples, without intending to restrict the scope of the present invention thereto.
Example 1 A 800 ml-stainless steel container was charged with given amounts of water and asphalt ("STRAIGHT ASPHALT,"
according to JIS K-2207, manufactured by Cosmo Oil Co.;
penetration: 80 to 100), and at least one of surfactants and stabilizers shown in Tables 1 to 6, and the ingredients were heated to a given temperature of 80~C in a thermostat. Thereafter, the mixture in the container was mixed in advance using an agitator equipped with CA 0220~294 1997-0~-14 double, helical ribbon blades for 5 minutes at a rotational speed of 60 r.p.m., and then the resulting mixture was blended and emulsified using a "T.K. HOMO
MIXER, Model M" (equipped with low-viscosity agitating blades; manufactured by Tokushu Kika Kogyo) to produce an emulsion fuel under the following conditions. Here, the emulsion fuel prepared above is referred to as "concentrated (conc.) emulsion," and this step is referred to as "Step (i)."
The agitation conditions are as follows.
Agitation rotational speed: 8000 r.p.m.
Agitation time: 2 minutes.
Temperature: 80~C.
Shear rate: 12000/sec.
Here, the specific gravity of water is 0.997 (25~C), and the specific gravity of oil is 1.026 (25~C). The viscosity is measured by using a double, cylindrical rotational viscometer "RV-2" (equipped with a sensor "MV-1," manufactured by Haake Co.) at 25~C while applying a shearing rate of 100/sec.
The particle size of the oil droplets of the obtained emulsion fuel is evaluated by using a granulometer "HR850-B" (manufactured by Cyrus Co.) to determine 50%-cumulative particle size (average particle diameter).
CA 0220~294 1997-0~-14 Specifically, the particle size is evaluated by the following method. Several droplets of the emulsion fuel are added in an aqueous solution containing 0.3% by weight of a nonionic surfactant (polyoxyethylene(20 mol) nonyl phenyl ether), and the resulting mixture is agitated using a stirrer, to provide a homogeneous liquid mixture. The homogeneous liquid mixture obtained above is placed in a granulometer to evaluate granularity. The measurement mode is set at 1 to 600 ,um.
The amount of coarse particles is evaluated by measuring the components having particle sizes of 150 ,um or more using a wet sieve. Specifically, 20 g of each the emulsion fuels is weighed and then poured on the sieve.
After rinsing the mesh-on particles with water, they are dried with a vacuum dryer. The amount of the particles remaining on the sieve after drying is measured to calculate the amount of coarse particles.
Next, given amounts of water heated at 80~C and an ionic dispersant listed in Table 1 to 6 were added to the concentrated emulsion prepared above. The mixture in the container was mixed in advance using an agitator equipped with double, helical ribbon blades for 5 minutes at a rotational speed of 60 r.p.m. Thereafter, the resulting mixture was blended and emulsified using a "T.K. HOMO
MIXER, Model M" (manufactured by Tokushu Kika Kogyo) to CA 0220~294 1997-0~-14 produce a desired emulsion fuel under the following conditions. Here, this step is referred to as "Step ( ii ) . "
The agitation conditions are as follows:
Agitation rotational speed: 3000 r.p.m.
Agitation time: 2 minutes.
Temperature: 80~C.
Shear rate: 4500/sec.
Inventive Sample Nos. 1 to 29 thus prepared are shown in Table 1 to 6. Here, except for Inventive Sample No. 29 where it was prepared by a method which was different from method of preparing the remaining Inventive Samples in that Step (ii) was carried out at 25~C, and Inventive Samples were all prepared under the same conditions. The average particle diameter immediately after the preparation and the amount of coarse particles were measured in the same manner as above.
Also, the obtained emulsion fuel is stored for a long term (three months), and emulsion stability after three month is evaluated by the amount of sediments, and the emulsion stability is determined by the following standards:
o: Very excellent;
c: Good;
~: Slight effect; and x: No effects.
In the tables, carboxymethylcellulose is abbreviated as "CMC."
CA 0220~294 1997-0~-14 Tab 1 e Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) (~ m) (wt%) Polyoxyethylene nonylphenyl ether l(HLB 15.5) 0.30wt% 2800 77 15.3 0.5 C M C 0.02wt%
Polyoxyethylene nonylphenyl ether 2(HLB 15.5) 0.30 wt% 2900 78 14.8 0.4 C M C O . 005wt%
Polyoxyethylene nonylphenyl ether 3(HLB 15.5) 0.30 wt% 2000 78 14.1 0.7 C M C 0.003wt%
Polyoxyethylene nonylphenyl ether 2500 75 13.0 0.3 4(HLB 15.5) 0.30wt%
C M C 0.10wt%
Polyoxyethylene nonylphenyl ether 2800 75 15.3 0.5 5(HLB 15.5) 0.30wt%
C M C 0.02wt%
CA 0220~294 1997-0~-14 Tab 1 e 1 (Cont i nued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp)(wt%) (~ m) (wt%) Mons.) Formalin Condensate of Sodium Naphtha-1 lenesulfonate 340 75 15.2 1.5 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-2 lenesulfonate 270 75 14.7 0.4 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-3 lenesulfonate 250 75 14.9 0.8 0 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-4 lenesulfonate 390 74 12.7 0.3 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-lenesulfonate 350 75 15.3 0.4 (Degree of Conden-sation: 10.2) 0.02wt%
CA 0220~294 1997-0~-14 Tab 1 e 2 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) ( ~ m ) (wt%) Polyoxyethylene nonylphenyl ether 6(HLB 15.5) 0.30wt% 2800 75 15.3 0.5 C M C O . 02wt%
Polyoxyethylene nonylphenyl ether 7(HLB 15.5) 0.30wt% 2800 77 15.3 0.5 C M C O . 02wt%
Polyoxyethylene nonylphenyl ether 8(HLB 15.5) 0.30wt% 2800 77 15.3 0.5 Xanthan gum 0.02wt%
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
9 2100 77 15.4 0.7 Polyvinylpyrrolidone (Molecular weight:
100000) 0.02wt%
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
2200 77 15.5 0.8 Polyvinyl Alcohol (Molecular weight:
100000) 0.02wt~
CA 0220~294 1997-0~-14 Tab 1 e 2 (Cont inued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt%) Mons.) Formalin Condensate of Sodium Naphtha-6 lenesulfonate 320 75 15.5 0.7 (Degree of Conden-sation: 10.2) 0.10wt~
Formalin Condensate of Sodium Naphtha-7 lenesulfonate 290 75 16.2 1.1 0 (Degree of Conden-sation: 10.2) 0.20wt%
Formalin Condensate of Sodium Naphtha-8 lenesulfonate 350 75 15.2 0.6 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-9 lenesulfonate 300 75 15.3 0.8 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-lenesulfonate 310 75 15.6 0.8 (Degree of Conden-sation: 10.2) 0.05wt%
CA 0220~294 1997-0~-14 Table 3 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt~) Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
11 2000 77 15.5 0.9 Polyvinylacrylamide (Molecular weight:
100000) 0.02wt~
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt~
1900 77 15.7 1.0 12Montmorilonite (Average Particle Size: 1.5 ~ m ) 0.05wt~
Polyoxyethylene nonylphenyl ether 13(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C O . 02wt%
Polyoxyethylene nonylphenyl ether 14(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 15(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
CA 0220~294 1997-0~-14 Tab 1 e 3 (Con t i nu e d) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate of Sodium Naphtha-11 lenesulfonate 300 75 15.7 1.O
(Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-12 lenesulfonate 280 75 15.8 1.1 (Degree of Conden-sation: 10.2) 0.05wt%
Sodium lignin-13 sulfonate 350 75 15.2 0.5 0.05wt~
Sodium polystyrene-14 sulfonate 370 75 15.2 0.6 0.05wt~
Sodium dodecyl benzenesulfonate 330 75 15.3 0.5 0.05wt%
CA 0220~294 1997-0~-14 Tab 1 e 4 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) ( ~ m) (wt~) Polyoxyethylene nonylphenyl ether 16(HLB 15.5) 0.40wt~ 2800 77 12.0 0.4 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 17(HLB 15.5) 0.80wt~ 3500 77 8.0 0.3 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 18(HLB 15.5) 0.20wt~ 2900 77 18.2 2.6 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 19(HLB 15.5) 0.10wt~ 3700 77 19.4 5.8 C M C o . 02wt~
Polyoxyethylene nonylphenyl ether 20(HLB 15.5) 0.30wt~ 2800 77 15.0 0.6 C M C 0.02wt~
CA 0220~294 1997-0~-14 T a b 1 e 4 ( C o n t i n u e d ) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate of Sodium Naphtha-16 lenesulfonate 350 75 12.2 0.4 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-17 lenesulfonate 950 75 8.0 0.3 A
(Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-18 lenesulfonate 550 75 18.4 2.6 O
(Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-19 lenesulfonate 720 75 19.5 5.9 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-lenesulfonate 360 75 15.1 0.6 (Degree of Conden-sation: 10.2) 0.05wt~
CA 0220~294 1997-0~-14 Tab 1 e 5 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt%) Polyoxyethylene dodecylphenyl ether 21(HLB 15.5) 0.30wt~ 2700 77 14.9 0.5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 22(HLB 15.5) 0.30wt~ 2600 77 16.6 2.0 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 23(HLB 15.5) 0.30wt~ 2700 77 15.8 0.9 C M C 0.02wt~
Polyoxyethylene oleyl ether 24(HLB 15.5) 0.30wt~ 2200 77 19.5 4.8 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 25(HLB 15.5) 0.30wt~ 2200 76 15.5 0.6 C M C 0.05wt~
CA 0220~294 1997-0~-14 Tabl e 5 (Cont inued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate of Sodium Naphtha-21 lenesulfonate 340 75 15.0 0.6 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-22 lenesulfonate 290 75 16.7 2.1 0 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-23 lenesulfonate 330 75 15.7 1.0 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-24 lenesulfonate 280 75 13.5 4.9 0 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-lenesulfonate 180 70 15.6 0.5 (Degree of Conden-sation: 10.2) 0.05wt~
CA 0220~294 1997-0~-14 T a b l e 6 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt~) Polyoxyethylene nonylphenyl ether 26(HLB 15.5) 0.30wt~ 2300 79 16.2 1.3 C M C O . 05wt~
Polyoxyethylene nonylphenyl ether 27(HLB 15.5) 0.30wt~ 2900 81 18.4 2.0 C M C O . 05wt~
Polyoxyethylene nonylphenyl ether 28(HLB 15.5) 0.30wt~ 890 79 15.4 1.3 CMC O wt~
Polyoxyethylene nonylphenyl ether 29(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
CA 0220~294 1997-0~-14 Tab 1 e 6 (Cont i nued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp)(wt%) (J' m) (wt%) Mons ) Formalin Condensate of Sodium Naphtha-980 78 16.2 1.3 26 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-270 75 18.5 2.1 27 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-210 75 15.3 2.8 28 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-390 75 15.3 1.7 29 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt%
CA 0220~294 1997-0~-14 Example 2 Step (i) was carried out in the same manner as in Example 1, to give concentrated emulsion. In step (ii), water and an ionic dispersant were added to the resultant emulsion. The mixture was agitated in the same manner as in Example 1, and then the resulting mixture was blended and emulsified using a "T.K. HOMO MIXER, Model M"
(manufactured by Tokushu Kika Kogyo) to produce an emulsion fuel under the agitation conditions given in Tables 7 and 8.
The resulting emulsion fuel was evaluated in the same manner as in Example l, and the physical properties are also shown in Tables 7 and 8. Inventive Sample Nos. 30 to 35 are cases where an ionic dispersant and water are added; Inventive Sample Nos 36 to 39 are cases where only concentrated aqueous solution of at least one ionic dispersant is added without adding optional water in step (ii) .
Also, in order to maintain viscosity in step (i), the procedures of step (ii) were carried out at 80~C. As for Inventive Samples 36 to 39 of Table 8, the viscosity of step (i) was measured at 80~C.
CA 0220~294 1997-0~-14 Tabl e 7 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt%) Polyoxyethylene nonylphenyl ether 30( HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 31( HLB 15 . 5 ) O . 30wt~ 2800 77 15 . 3 0. 5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 32( HLB 15 . 5 ) O . 30wt% 2800 77 15 . 3 O. 5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 33( HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 34( HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
Tab 1 e 7 (Cont inued) Step (ii) Desired Emulsion Product Shear Inventive Ionic C,ondi-Conc. of Sta-Sample Di~ ,tstions Visco- Super- Average C,oarse bility Nos. of Step sity heavy Particle Parti- (After (ii) Oil Size cles Three (cp)(wt%) (J~ m) (wt%) Mons.) Formalin Crn~nqate of Sodium Naphtha-lenesulfonate 1200/s 420 75 15.2 0.6 (Degree of Conden-sation: 10.2) 2 min.
0.075wt~
Formalin C~n~Pnq~te of Sodium Naphtha-31 lenesulfonate 600/s 900 75 15.3 0.6 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
Formalin C,ondensate of Sodium Naphtha-32 lenesulfonate 3000/s 350 75 15.2 0.6 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
Formalin Cm ~nqate of Sodium Naphtha-33 lenesulfonate 6000/s 340 75 15.1 0.7 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
Formalin Condensate of Sodium Naphtha-34 lenesulfonate 12000/s 320 75 15.6 1.5 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
CA 0220~294 1997-0~-14 Tabl e 8 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) ( ~ m) (wt%) Polyoxyethylene nonylphenyl ether 35(HLB 15.0) 0.40wt~ 1500 78 15.2 0.3 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 36(HLB 15.0) 0.40wt~ 1500 78 15.2 0.3 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 37(HLB 15.0) 0.40wt% 1900 79 15.8 0.4 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 38(HLB 15.0) 0.40wt~ 2200 80 17.5 1.4 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 39(HLB 15.0) 0.40wt% 2200 80 17.5 1.4 C M C 0.01wt%
T a b 1 e 8 (C o n t i n u e d) Step (ii) Desired Emulsion Product Shear Inventive Ionic Condi-Conc. of Sta-Sample Dispersants tions Visco- Super- Average Ccarse bility Nos. of Step sity heavy Particle Parti- (After (ii) Oil Size cles Three (cp)(wtO (~ m) (wt O Mons.) Sodium lignin-35sulfonate 1200/9 631 77 15.2 0.7 0.075wt~ 2 min.
Sodium lignin-36sulfonate 1200/s 433 77 15.3 0.3 0.10 wt~ 2 min.
Sodium lignin-37sulfonate 1200/s 620 78 15.2 0.5 0.15 wt% 2 min.
Sodium lignin-38sulfonate 1200/s 840 79 17.4 1.4 0.20 wt~ 2 min.
Sodium lignin-sulfonate 390.20 wt~ 1200/s 950 79 17.6 1.5 CMC 0.0C5wt~ 2 min.
CA 0220~294 1997-0~-14 Comparative Example The same procedures as in Example 1 were carried using at least one of surfactants and stabilizers shown in Table 9, to give Comparative Samples 1 to 4.
The physical properties are evaluated in the same manner as in Example 1, and the results are also shown in Table 9. The physical properties of Comparative Sample No. 3 could not be evaluated, because no emulsion was formed in this sample.
CA 0220~294 1997-0~-14 Tab 1 e 9 Step (i) Thick Emulsion Fuel Comparative Surfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m ) (wt~) Polyoxyethylene nonylphenyl ether 1(HLB 12.5) 0.30wt% > 3500 77 18.5 7.5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 2(HLB 19.3) 0.30wt~ > 3500 79 20.4 6.6 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 3(HLB 15.5) 0.05wt~
C M C 0.02wt~
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
C M C O . 02wt~
4Formalin Condensate 290 75 16.1 6.1 of Sodium Naphtha-lenesulfonate (Degree of Conden-sation: 10.2) 0.075wt~
CA 0220~294 1997-0~-14 Tab 1 e 9 (Cont inued) Step (ii) Desired Emulsion Product Comparative Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate l of Sodium Naphtha- > 3500 75 18.5 7.5 X
lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate 2 of Sodium Naphtha- >3500 75 21.0 6.8 X
lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt~
CA 0220~294 1997-0~-14 -- 70 -- .
As is clear from Tables 1 to 10, when compared with the comparative samples, all of the emulsion fuels of the inventive samples prepared according to the method of the present invention have smaller amount of coarse particles and excellent flowability and long-term storage ability.
The present invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be explained in detail below.
The method for producing superheavy oil emulsion fuel of the present invention comprises two steps, namely step (i) and step (ii). The method of the present invention will be described in detail for each step (i) and step ( ii ) .
1. Step (i) Step (i) comprises preparing a liquid mixture comprising a superheavy oil, water, one or more nonionic surfactants having an HLB (hydrophilic-lipophilic balance) of 13 to 19, and optionally one or more stabilizers, and then agitating the resulting liquid mixture with a high shear rate of 1000/sec to 60000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 74 to 82~ by weight, wherein the nonionic surfactants are contained in an amount of from 0.1 to 0.8~ by weight of the emulsion fuel obtained in step (i), and wherein the stabilizers, when added, are contained in an amount of from 0.001 to 0.5~ by weight of CA 0220~294 1997-0~-14 the emulsion fuel obtained in step (i).
The "superheavy oil" usable in the present invention refers to those in a solid or semi-fluid state at room temperature, which do not flow unless heated to a high temperature. Examples of the superheavy oils include the following:
(1) Petroleum asphalts and mixtures thereof;
(2) Various treated products of petroleum asphalts, intermediates, residues, and mixtures thereof.
(3) High pour point-oils which do not even flow at high temperatures, or crude oils;
(4) Petroleum tar pitches and mixtures thereof; and (5) Bitumens (Orinoco tar and athabasca bitumen).
Examples of the nonionic surfactants usable in the present invention include the following ones:
(i) Alkylene oxide adducts of compounds having phenolic hydroxyl groups, such as phenol, m-cresol, butylphenol, octylphenol, nonylphenol, dodecylphenol, p-cumylphenol, and bisphenol A.
(ii) Alkylene oxide adducts of formalin (formaldehyde) condensates of compounds having phenolic hydroxyl groups, such as alkylphenols, phenol, m-cresol, styrenated phenol, and benzylated phenol, wherein the average degree of condensation is 1.2 to 100, preferably 2 to 20.
CA 0220~294 1997-0~-14 (iii)Alkylene oxide adducts of aliphatic alcohols and/or aliphatic amines each having 2 to 50 carbon atoms.
(iv) Block or random addition polymers of ethylene oxide/propylene oxide, ethylene oxide/butylene oxide, ethylene oxide/styrene oxide, ethylene oxide/propylene oxide/butylene oxide, ethylene oxide/propylene oxide/ethylene oxide, and ethylene oxide/propylene oxide/styrene oxide.
(v) Alkylene oxide adducts of polyhydric alcohols, such as glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerols, ethylene glycol, polyethylene glycols, propylene glycol, and polypropylene glycols, or those of esters formed between the above-described polyhydric alcohols and fatty acids having 8 to 18 carbon atoms.
(vi) Alkylene oxide adducts of polyvalent amines having a plurality of active hydrogen atoms, such as ethylenediamine, tetraethylenediamine, and polyethyleneimine (weight-average molecular weight:
600 to 10,000).
(vii)Products formed by addition reaction of alkylene oxides with a mixture comprising one mol of fats and oils comprising triglyceride and 0.1 to 5 mol of one or more polyhydric alcohols and/or water, the CA 0220~294 1997-0~-14 polyhydric alcohol being at least one member selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylene glycol, polyethylene glycols having a weight-average molecular weight of 1000 or less, propylene glycol, and polypropylene glycols having a weight-average molecular weight of 1000 or less.
In each of the nonionic surfactants (i) to (vii), the alkylene oxide means, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and combinations thereof.
In the present invention, the nonionic surfactants may be used alone or in combination of two or more kinds.
Among the above nonionic surfactants, a preference is given those listed under item (i), specifically, alkylene oxide adducts of compounds having phenolic hydroxyl groups, such as octylphenol, nonylphenol, and dodecylphenol.
The nonionic surfactants usable in the present invention have an HLB of usually from 13 to 19, preferably from 13.5 to 15.5. The HLB of the nonionic surfactants is from 13 to 19 in order to obtain stable emulsion. The "HLB" values in the present invention refer to an abbreviation of a hydrophilic-lipophilic balance calculated from the Griffin's equation. Specifically, the CA 0220~294 1997-0~-14 HLB is an index for surface activity by expressing intensity ratios between a hydrophilic property and a lipophilic property of amphiphilics. Here, the found values of Griffin et al. are employed (W.C. Griffin, "Kirk-Othmer Encyclopedia of Chemical Technology," 3rd Ed., Vol. 8, p.913-916, John-Wiley (1979)).
The nonionic surfactant in the present invention used is contained in an amount of from 0.1 to 0.8% by weight, preferably from 0.2 to 0.4% by weight, of the emulsion fuel obtained in step (i). The amount is preferably 0.8%
by weight or less, from the aspect of maintaining good particle size of the oil particles in the resulting emulsion fuel without being too small, and the amount is preferably 0.1% by weight or more, from the aspect of maintaining good particle size of the oil particles without being too large as well as having good emulsion stability by the sufficient inclusion of the surfactants.
In the preparation of the liquid mixture in step (i), in addition to the nonionic surfactants, commercially available anionic surfactants and cationic surfactants may be optionally added to the liquid mixture, a weight ratio of the optional surfactants to the nonionic surfactant being preferably from 1/100 to 1/4, more preferably from 1/20 to 1/5.
Examples of the anionic surfactants usable in the CA 0220~294 1997-0~-14 present invention include the following ones.
(i) Sulfonates of aromatic ring compounds, such as naphthalenesulfonates, alkylnaphthalenesulfonates, alkylphenolsulfonates, and alkylbenzenesulfonates, or formalin (formaldehyde) condensates of sulfonates of aromatic ring compounds, wherein the average degree of condensation of formalin is from 1.2 to 100, more preferably from 2 to 20, and wherein the sulfonates are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(ii) Lignin sulfonic acid, salts thereof, or derivatives thereof, formalin (formaldehyde) condensates of lignin sulfonic acid and sulfonic acids of aromatic compounds, such as naphthalenesulfonic acid and alkylnaphthalenesulfonic acids, and salts thereof, wherein the salts for both the lignin sulfonates and the sulfonates of aromatic compounds are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or CA 0220~294 1997-0~-14 alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts, and wherein the average degree of condensation of formalin is from 1.2 to 50, preferably from 2 to 20.
Among the lignins, excellent performance at high temperatures can be particularly achieved when a modified lignin, for instance, those substituted by one or more carboxyl groups, is used.
(iii)Polystyrenesulfonic acids or salts thereof, copolymers of styrenesulfonic acid with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified hy ammonium salts;
lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Here, typical examples of the copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, acrylic ester, olefins, allyl alcohols and ethylene oxide adducts thereof, and acrylamide methylpropylsulfonic acid.
(iv) Polymers of dicyclopentadienesulfonic acid or CA 0220~294 l997-0~-l4 salts thereof, wherein the weight-average molecular weight of the polymers is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(v) Copolymers of maleic anhydride and/or itaconic anhydride with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 1,500 to 100,000, and wherein the salts are exemplified by ammonium salts; and alkali metal salts, such as sodium salts and potassium salts. Here, typical examples of the copolymerizable monomers include olefins, such as ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and hexadecene, styrene, vinyl acetate, acrylic ester, acrylic acid, and methacrylic acid.
(vi) Maleinized liquid polybutadienes or salts thereof, wherein the weight-average molecular weight of the liquid polybutadienes as the starting CA 0220~294 l997-0~-l4 materials is from 500 to 200,000, preferably from 1,000 to 50,000, and wherein the degree of maleinization is at a level necessary for dissolving the maleinized liquid polybutadiene in water, preferably from 40 to 70%, and wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(vii)Anionic surfactants having in the molecule one or two hydrophilic groups, selected from the following (a) to (h):
(a) Sulfuric ester salts of alcohols having 4 to 18 carbon atoms, wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecyl sulfate and sodium octyl sulfate.
(b) Alkanesulfonic acids, alkenesulfonic acids, and/or alkylarylsulfonic acids, each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, CA 0220~294 l997-0~-l4 diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecylbenzene sulfonate, sodium butylnaphthalene sulfonate, and sodium dodecane sulfonate.
(c) Sulfates or phosphates of alkylene oxide adducts of compounds having in the molecule one or more active hydrogen atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Typical examples thereof include sulfuric ester sodium salts of polyoxyethylene(3 mol) nonyl phenyl ether, and phosphoric ester sodium salts of polyoxyethylene(3 mol) dodecyl ether.
(d) Sulfosuccinic ester salts of saturated or unsaturated fatty acids having 4 to 22 carbon atoms, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Typical examples thereof include sodium CA 0220~294 1997-0~-14 dioctylsulfosuccinate, ammonium dioctylsulfosuccinate, and sodium dibutylsulfosuccinate.
(e) Alkyldiphenylether disulfonic acids or salts thereof, of which the alkyl group has 8 to 18 carbon atoms, and wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(f) Rosins or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Examples thereof include mixed tall acids comprising a tall rosin and a higher fatty acid, and salts thereof.
(g) Alkanefatty acids or alkenefatty acids each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(h) a-Sulfofatty ester salts of which the alkyl group has 4 to 22 carbon atoms and derivatives thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or CA 0220~294 1997-0~-14 alkaline earth metal salts, such as sodium salts, potassium salts, and magnesium salts.
Among the anionic surfactants listed above, a preference is given to the lignin sulfonates, the formalin condensates of lignin sulfonic acid and the formalin condensates of naphthalenesulfonic acid or salts thereof, and the formalin condensates of naphthalenesulfonates because they show overall superior performance in charging the particles.
The cationic surfactants usable in the present invention are the following ones.
(i) Alkylamine salts and/or alkenylamine salts obtainable by neutralizing an alkylamine or alkenylamine, each of alkyl or alkenyl group having 4 to 18 carbon atoms, with an inorganic acid and/or an organic acid, such as hydrochloric acid and acetic acid.
(ii) Quaternary ammonium salts represented by the following general formulae (A), (B), and (C):
R2 ' ~
R,-- I -- R 4 X- (A) wherein R1, R2, R3, and R4, which may be identical or different, independently stand for an alkyl group or CA 0220~294 1997-0~-14 alkenyl group, each having 1 to 18 carbon atoms; and X~ stands for a counter anion, including chlorine ion or bromine ion;
R2 ' +
R, -N -- R3 X- (B) [~
wherein R1, R2, R3, and X~ are as defined above; and +
X- (C) wherein Rs stands for an alkyl group or alkenyl group having 8 to 18 carbon atoms; R6 stands for a hydrogen atom or a methyl group; and X~ is as defined above.
(iii)Alkylbetaines or alkenylbetaines represented by the following general formula:
,CH3 R- +N- CH3 \CH2 C00-wherein R stands for an alkyl group or alkenyl group, 2 5 each having 8 to 18 carbon atoms.
CA 0220~294 1997-0~-14 (iv) Alkylamine oxides or alkenylamine oxides represented by the following general formula:
R--N ~ 0 wherein R is as defined in item (iii).
(v) Alkylalanines or alkenylalanines represented by the following general formula:
R- +NlCH2 CH2 C00-\C H3 wherein R is as defined in item (iii).
(vi) Alkylene oxide adduct polymers of diamine or triamine represented by the following general formula (D) or (E):
RNH C 3 H6 NHY (D) y RNHC3 H6 N < (E) y wherein R is as defined in item (iii); and Y and Y', which may be identical or different, each stands for an oxyethylene moiety represented by the general CA 0220~294 1997-0~-14 formula:
i C2 H4 O) m H
wherein m stands for a number of from 1 to 50.
(vii)Polyamine salts represented by the following formula (F) or (G):
RNHC3 H6 NHX' (F) RNH (C3 H6 NH)2X' (G) wherein R is as defined in item (iii); and X' stands for an inorganic acid or organic acid, such as hydrochloric acid and acetic acid.
Examples of stabilizers which may be used in combination with the nonionic surfactants in step (i) include (l) polymeric compounds, including naturally occurring polymers and synthetic polymers, and (2) water-swellable clay minerals. In other words, the stabilizers usable in the present invention may be selected from items (1) and (2) listed below.
(1) Polymeric Compounds Hydrophilic Naturally Occurrinq Polymers Derived from Naturally Occurrinq Substances CA 0220~294 1997-0~-14 -- Hydrophilic Polymers Derived from Microorganism (Polysaccharides) 1) Xanthan gum 2 ) Pullulan 3) Dextran -- Hydrophilic Polymers Derived from Plants (Polysaccharides) 1) Derived from marine algae: agar, carrageenan, furcellaran, alginic acid and salts (Na, K, NH4, Ca, or Mg) thereof 2) Derived from seeds: locust bean gum, guar gum, tara gum 3) Trees (exudates): gum arabic, gum karaya, gum tragacanth; and 4) Derived from fruits: pectin -- Hydrophilic Polymers Derived from Animals (Proteins) 1) Gelatin 2) Casein -- Naturally Occurring Polymer Derivatives 1) Cellulose derivatives, such as carboxymethylcellulose 2) Chemically modified starch Water-Soluble Synthetic Polymers CA 0220~294 1997-0~-14 (a) Homopolymers or copolymers of acrylic acidor derivatives thereof represented by the following general formula:
~ R' CH2 -C Z, ) C O2 Ml /n wherein R' stands for a hydrogen atom, a methyl group, or an ethyl group; M1 stands for a hydrogen atom, a sodium ion, a potassium ion, a lithium ion, or an ammonium ion; Z1 stands for a divalent group which is derived from a monomer and salts thereof copolymerizable therewith, the divalent group being represented by the following general formula:
CO2 M, wherein R' and M1 are as defined above, wherein the salts of the copolymerizable monomers are exemplified by ammonium salts, sodium salts, potassium salts, and lithium salts; and n stands for a number of from 50 to CA 0220~294 1997-0~-14 100,000. Examples of the copolymerizable monomers include maleic acid (anhydride), itaconic acid (anhydride), a-olefins, acrylamide, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, and acrylamidomethylpropylsulfonic acid, and salts thereof, including ammonium salts, sodium salts, potassium salts, and lithium salts; dialkyl aminoethyl methacrylates, such as dimethyl aminoethyl methacrylate and diethyl aminoethyl methacrylate and salts thereof, including halogenides, such as chloride, diethyl sulfate, and dimethyl sulfate.
(b) Homopolymers or copolymers of acrylamide or derivatives thereof represented by the following general formula:
CH2 -CH-Z2 ) n Cl O
NH
R~
wherein R" stands for a hydrogen atom or a C2H40H
group; Z2 stands for a divalent group which is derived from a monomer or salts thereof, the divalent group being represented by the CA 0220~294 1997-0~-14 following general formula:
Cl O
NH
R
wherein R" is as defined above, and wherein the salts of the copolymerizable monomers are exemplified by ammonium salts, sodium salts, potassium salts, and lithium salts; and n stands for a number of from 50 to 100,000. Examples of the copolymerizable monomers include vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, acrylamidomethylpropylsulfonic acid, and salts thereof, including ammonium salts, sodium salts, potassium salts, and lithium salts; dialkyl aminoethyl methacrylates, such as dimethyl aminoethyl methacrylate and dimethyl aminoethyl methacrylate and salts thereof, quaternary compounds thereof, including halogenides, such as chloride, diethyl sulfate, and dimethyl sulfate; styrene; a-olefins having 2 to 18 carbon atoms; and vinylallyl alcohols.
( C ) Homopolymers of maleic anhydride or CA 0220~i294 1997~0~i~14 -- 26 ~
itaconic anhydride, or copolymers thereof represented by the following general formula:
( M2-- Z3 ) n wherein M2 stands for a maleic anhydride unit or itaconic anhydride unit; Z3 stands for an a-olefin unit, the a-olefins including ethylene, propylene, butylene, isobutylene, octene, decene, and dodecene, or a styrene unit; and n stands for a number of from 50 to 100,000.
(d) Polyvinyl alcohols or copolymers thereof represented by the following general formula:
~CH2 --CH -- Z~
~ OH Jn wherein Z4 stands for a vinyl acetate unit or styrene unit; and n' stands for a number of from 30 to 100,000.
( e) Homopolymers of vinylpyrrolidone, or copolymers thereof represented by the following general formula:
CA 0220~294 1997-0~-14 CH2 -Cl H Z6) N O n / \~
wherein Zs stands for a divalent group which is derived from a monomer copolymerizable with a vinylpyrrolidone monomer, wherein the salts of the monomers copolymerizable with vinylpyrrolidone monomers include ammonium salts, sodium salts, potassium salts, and lithium salts. Examples of the monomers copolymerizable with the vinylpyrrolidone monomer or salts thereof include acrylamide, vinylsulfonic acid, methallylsulfonic acid, maleic anhydride, itaconic anhydride, and salts thereof, such as ammonium salts, sodium salts, potassium salts, and lithium salts; styrene;
~-olefins having 2 to 18 carbon atoms; and n stands for a number of from 50 to 100,000.
(f) Polyalkylene oxides having a weight-average molecular weight of from 10,000 to 5,000,000, wherein the ethylene oxide content is 95~ by weight or more, which may include those containing in the molecule 5~ by weight or less CA 0220~294 1997-0~-14 of various block polymers of propylene oxide, butylene oxide, and styrene oxide or alkylallyl groups or alkyl groups.
Among these polymeric compounds, naturally occurring polymeric derivatives, including cellulose derivatives, such as carboxymethylcellulose, and hydrophilic polymers derived from microorganism, such as xanthan gum, are suitably used in the present invention.
(2) Water-Swellable Clay Minerals The water-swellable clay minerals usable in the present invention include the following ones.
The clay minerals usable in the present invention is a highly swellable fine clay mineral, wherein the term "highly swellable" clay minerals refer to those bound with a large amount of water molecules when the clay minerals are suspended in water, so as to have a relaxation time (T2) for water molecules of preferably from 900 msec or less, more preferably 500 msec or less, the relaxation time for water molecules being measured by a nuclear magnetic resonance spectrometer when the clay minerals are suspended in water in an amount of 1% by weight on a dry basis. When the relaxation time for the water molecules is 900 msec or less, a good binding force of the clay minerals to the water molecules can be maintained, thereby CA 0220~294 1997-0~-14 making it possible to sufficiently attain the effects of the present invention. In addition, the term "fine clay mineral" refers to the clay minerals having an average particle size of preferably from 100 ,um or less. The clay 5 mineral has an average particle size of preferably 100 ,um or less, a good binding force of the clay minerals to the water molecules can be maintained, and at the same time sedimentation of the clay minerals is liable to be inhibited, thereby making it possible to sufficiently attain the effects of the present invention.
Specifically, the fine clay minerals having a high swellability and a high binding force to the water molecules, including smectites, vermiculites, and chlorites, fall within the scope of the present invention.
Among them, however, those having a T2 value exceeding 900 msec are outside the scope of the present invention.
Further, since kaolin produced in Georgia, U.S.A., general kaolin and talc have weak binding forces to the water molecules, they are excluded from the scope of the present 20 invention.
The highly swellable fine clay minerals, such as smectites, vermiculites, and chlorites, usable in the present invention will be explained in detail below.
(A) Smectite has a complicated chemical composition 25 comprising two tetrahedral sheets and one octahedral sheet CA 0220~294 1997-0~-14 inserted therebetween (namely a 2:1 layer), because substitution takes place in a wide range and various ions accompanied by water molecules are intercalated. The smectite is represented by, for example, the following general formula:
Xm(Y ,Y )23Z401o(0H)2 ~ nH20, wherein X stands for K, Na, 1/2Ca, or 1/2Mg; y2+ stands for Mg2+, Fe2+, Mn2+, Ni2+, Zn2+, or Li, Y3+ stands for Al3+, Fe3+, Mn3+, or Cr3+; and Z stands for Si and/or Al, with proviso that X, Y, and Z stand for an intercalated cation, an octahedral cation, and a tetrahedral cation, respectively.
Typical examples of the smectites are the following ones:
Dioctahedral (octahedral cations being mainly trivalent):
Montmorillonites represented by, for example, the following formula:
xo33(All67Mgo33)si4olo(OH)2 ~ nH20;
Beidellites represented by, for example, the following formula:
X033( Al2 ) ( Alo 33Si3 67 ) ~10 ( OH)2 ~ nH20; and Nontronites represented by, for example, the following formula:
XO33(Fe(III)2)(Alo33si3 67)~lO(OH )2 ~ nH2~' 25 Trioctahedral (octahedral cations being mainly divalent):
CA 0220~294 l997-0~-l4 Saponites represented by, for example, the following formula:
XO33(Mg3)( Alo 33si3.67)~10(OH)2 ~ nH20;
Iron saponites represented by, for example, the following formula:
XO33(Mg,Fe(II))3(Alo33si367)olo(oH)z nH20;
Hectorites represented by, for example, the following formula:
Xo.33(Mg267Lio33)Si4010(OH)2 ~ nH20;
Sauconites represented by, for example, the following formula:
Xo33(Mg~Zn)3(si367Al033)~lO(OH)2 ~ nH20; and Stevensites represented by, for example, the following formula:
XO.33/2(Mg297)s i4Ol0 ( OH)2 ~ nH20.
Among the smectites listed above, the montmorillonites, the beidellites, and the nontronites constitute a series which can be subjected to isomorphous substitution. The stevensites have layer charges of one-half of that of the other smectites, and thus having an intermediary property of the dioctahedral smectites and the trioctahedral smectites.
(B) Vermiculites pertain to 2:1 layer silicates and are represented by, for example, the following formula:
(Mg~Fe(III)~Al)23(si4xAlx)olo(oH)2(M~M2 1/2)X ~ nH2~' CA 0220~294 1997-0~-14 In the above formula, M stands for an intercalated exchangeable cation, and when the vermiculite is in the form of coarse particles, M is mainly composed of Mg. "n"
in the above formula stands for the amount of water, and when the intercalated cation is Mg, water forms a bimolecular layer over a wide temperature range and n is in the range of from about 3.5 to 5. "x" in the above formula stands for layer charges which are in the range of from 0.6 to 0.9.
In the above formula, it is assumed that all of the layer charges are generated by the substitution of tetrahedral cations. However, in certain cases, the octahedral sheet may actually carry a negative charge to which the layer charges are ascribed. The number of octahedral cations is 2 to 3, and the vermiculites are classified into dioctahedral vermiculites and trioctahedral vermiculites. The vermiculites in the form of coarse particles obtainable by the weathering of biotite and phlogopite are trioctahedral vermiculites.
(C) The structures of the chlorites are similar to those of the smectites and the vermiculites, and the base plane interval is 14 to 15~. The chlorites are typically a 2:1 hydrated silicate which can be classified into trioctahedral chlorites and dioctahedral chlorites depending on the properties of the 2:1 layer.
CA 0220~294 1997-0~-14 The trioctahedral chlorites are represented by, for example, the following formula:
(R6-x Rx )(si4-xAlx)~lO(OH) 8 .
In the above formula, R2+ is mainly composed of Mg2+
and Fe2+, which may also include Mn2+ and Ni2+; and R3+ is mainly composed of Al, which may also include Fe3+ and Cr3+. "x" in the above formula is a value of from 0.8 to 1.6.
A chlorite wherein R2+ is mainly composed of Mg2+ is so-called "clinochlore" [e.g. (MgsAl)(Si3Al)~10(OH )8]; and a chlorite wherein R2+ is mainly composed of Fe(II) is so-called "chamosite" [e.g. (FesAl)(Si3Al)~10(OH )8]
Examples of other trioctahedral chlorites include "pennantite" wherein R2+ is mainly composed of Mn(II); and "nimite" wherein R2+ is mainly composed of Ni(II).
The dioctahedral chlorites wherein the octahedral cation is mainly composed of Al are classified into the following three kinds.
Sudoite [e.g. (Mg,Al)465(si,Al)4~l0(oH)8;
Cookeite [e.g. (LiAl4)(Si3Al)~10(OH) 8; and Donbassite [e.g. Al442Ro2(si,Al)4~lO(oH)8 The clay minerals comprising montmorillonite, the clay mineral pertaining to smectite, as the main component, and further containing as impurities, quartz, a-cristobalite, opal, feldspar, mica, zeolite, calcite, CA 0220~294 1997-0~-14 dolomite, gypsum, and iron oxide are so-called "bentonite." The bentonites include sodium bentonite rich in Na ions and calcium bentonite rich in Ca ions. Since sodium bentonite has high swellability, it falls within the scope of the clay minerals of the present invention, while calcium bentonite has notably low swellability that it is excluded from the scope of the present invention.
These stabilizers are contained in an amount of from 0.001 to 0.5% by weight, preferably from 0.001 to 0.1% by weight, most preferably from 0.005 to 0.1% by weight, of the emulsion fuel obtained in step (i). The addition of the stabilizers allows to suppress the mobility in the interface of the oil droplets, so that the resulting emulsion fuels may be stabilized.
In addition, aside from the stabilizers mentioned above, at least one member selected from magnesium acetate, magnesium sulfate, magnesium nitrate, calcium acetate, calcium sulfate, calcium nitrate, iron acetate, iron sulfate, and iron nitrate is further added to the liquid mixture, may be added, to thereby give a good emulsion stability effect. In this case, these stabilizers are contained in an amount of from 0.01 to 0.2~ by weight, preferably from 0.05 to 0.1% by weight, of the emulsion fuel obtained in step (i).
In step (i), the agitators to be used when preparing a liquid mixture comprising a superheavy oil, water, a CA 0220~294 1997-0~-14 nonionic surfactant, and optional stabilizers are not particularly required to have high shear rates, and any one of general agitators, such as propeller agitators, will suffice. The agitation after the preparation of the liquid mixture needs to be carried out by agitators with high shear rates. Examples thereof include line mixers, arrow blade turbine blade mixers, full margin-type blade mixers, high-shear turbine mixers, and homogenizers. From the viewpoint of industrial efficiency, homomixers equipped with high-shear turbine mixers are preferably used. Here, the term "high shear rate" refers to a shear rate of from l,000/sec to 60,000/sec, preferably from 5,000/sec to 20, 000/sec. By agitating with such a high shear rate, the oil-in-water (0/W) type emulsion fuel having a concentration of the superheavy oil of from 74 to 82~ by weight, preferably from 77 to 81~ by weight. By agitating the liquid mixture with such a high shear rate, the oil-in water (0/W) emulsion fuel having a superheavy oil concentration of from 74 to 82% by weight, preferably 20 from 77 to 81~ by weight can be produced. The water is added in step (i) so as to make up 100~ by weight with the entire emulsion fuel, namely, the amount of water is from 17 to 25~ by weight.
The kinds and the amounts of the nonionic 25 surfactants, the shear rates, and time required for agitation of the liquid mixture, and viscosity during CA 0220~294 1997-0~-14 agitation have to suitably adjusted so that the oil-in-water (0/W) emulsion fuel obtained in step (i) has a particle size distribution wherein a 50%-cumulative particle size is preferably from 3 to 30 ,um, more preferably 8 to 20 ,um, and wherein coarse particles having particle sizes of 150 ,um or more occupy preferably 3~ by weight or less, more preferably 2% by weight or less, still more preferably 1~ by weight or less, in the entire emulsion fuel. The viscosity of the resulting oil-in-water emulsion fuel is preferably 400 c.p. or more (at 25~C), more preferably from 400 to 3000 C.p. (at 25~C). Incidentally, the term "particle size" used herein refers to particle diameter. The "particle size" and "amount of coarse particles" are evaluated by methods described in Examples which are set forth hereinbelow.
2. Step (ii) Step (ii) comprises adding at least one of water and ionic dispersants to the emulsion fuel obtained in step (i), and then blending and agitating the resulting liquid mixture with a shear rate of 10/sec to 10000/sec, to give an oil-in-water (0/W) type emulsion fuel having a superheavy oil concentration of from 68 to 79% by weight, wherein the ionic dispersants, when added, are contained in an amount of from 0.01 to 0.5% by weight of the emulsion fuel obtained in step (ii).
CA 0220~294 1997-0~-14 The ionic dispersants usable in step (ii) include the following anionic surfactants.
(i) Sulfonates of aromatic ring compounds, such as naphthalenesulfonates, alkylnaphthalenesulfonates, alkylphenolsulfonates, and alkylbenzenesulfonates, or formalin (formaldehyde) condensates of sulfonates of aromatic ring compounds, wherein the average degree of condensation of formalin is from 1.2 to lO0, more preferably from 2 to 20, and wherein the sulfonates are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(ii) Lignin sulfonic acid, salts thereof, or derivatives thereof, formalin (formaldehyde) condensates of lignin sulfonic acid and sulfonic acids of aromatic compounds, such as naphthalenesulfonic acid and alkylnaphthalenesulfonic acids, and salts thereof, wherein the salts for both the lignin sulfonates and the sulfonates of aromatic compounds are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and CA 0220~294 1997-0~-14 triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts, and wherein the average degree of condensation of formalin is from 1.2 to 50, preferably from 2 to 20.
Among the lignins, excellent performance at high temperatures can be particularly achieved when a modified lignin, for instance, those substituted by one or more carboxyl groups, is used.
(iii)Polystyrenesulfonic acids or salts thereof, copolymers of styrenesulfonic acid with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified by ammonium salts;
lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Here, typical examples of the copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, acrylic ester, olefins, allyl alcohols and ethylene oxide adducts thereof, and acrylamide methylpropylsulfonic acid.
CA 0220~294 1997-0~-14 (iv) Polymers of dicyclopentadienesulfonic acid or salts thereof, wherein the weight-average molecular weight of the polymers is from 500 to 500,000, preferably from 2,000 to 100,000, and wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(v) Copolymers of maleic anhydride and/or itaconic anhydride with other copolymerizable monomer(s), or salts thereof, wherein the weight-average molecular weight is from 500 to 500,000, preferably from 1,500 to 100,000, and wherein the salts are exemplified by ammonium salts; and alkali metal salts, such as sodium salts and potassium salts. Here, typical examples of the copolymerizable monomers include olefins, such as ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and hexadecene, styrene, vinyl acetate, acrylic ester, acrylic acid, and methacrylic acid.
(vi) Maleinized liquid polybutadienes or salts thereof, wherein the weight-average molecular weight CA 0220~294 1997-0~-14 of the liquid polybutadienes as the starting mate-rials is from 500 to 200,000, preferably from 1,000 to 50,000, and wherein the degree of maleinization is at a level necessary for dissolving the maleinized liquid polybutadiene in water, preferably from 40 to 70%, and wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(vii)Anionic surfactants having in the molecule one or two hydrophilic groups, selected from the following (a) to (h):
(a) Sulfuric ester salts of alcohols having 4 to 18 carbon atoms, wherein the salts are exemplified by ammonium salts; lower amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecyl sulfate and sodium octyl sulfate.
(b) Alkanesulfonic acids, alkenesulfonic acids, and/or alkylarylsulfonic acids, each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts; lower CA 0220~294 l997-0~-l4 amine salts, such as monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triethylamine salts; and alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts. Typical examples thereof include sodium dodecylbenzene sulfonate, sodium butylnaphthalene sulfonate, and sodium dodecane sulfonate.
(c) Sulfates or phosphates of alkylene oxide adducts of compounds having in the molecule one or more active hydrogen atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
Typical examples thereof include sulfuric ester sodium salts of polyoxyethylene(3 mol) nonyl phenyl ether, and phosphoric ester sodium salts of polyoxyethylene(3 mol) dodecyl ether.
(d) Sulfosuccinic ester salts of saturated or unsaturated fatty acids having 4 to 22 carbon atoms, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Typical examples thereof include sodium dioctylsulfosuccinate, ammonium CA 0220~294 1997-0~-14 dioctylsulfosuccinate, and sodium dibutylsulfosuccinate.
(e) Alkyldiphenylether disulfonic acids or salts thereof, of which the alkyl group has 8 to 18 carbon atoms, and wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, magnesium salts, and calcium salts.
(f) Rosins or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts. Examples thereof include mixed tall acids comprising a tall rosin and a higher fatty acid, and salts thereof.
(g) Alkanefatty acids or alkenefatty acids each having 4 to 18 carbon atoms, or salts thereof, wherein the salts are exemplified by ammonium salts, and alkali metal salts, such as sodium salts and potassium salts.
(h) a-Sulfofatty ester salts of which the alkyl group has 4 to 22 carbon atoms and derivatives thereof, wherein the salts are exemplified by ammonium salts, or alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts, and magnesium salts.
Among the anionic surfactants listed above, a CA 0220~294 1997-0~-14 preference is given to the lignin sulfonates, the formalin condensates of lignin sulfonic acid and the formalin condensates of naphthalenesulfonic acid or salts thereof, and the formalin condensates of naphthalenesulfonates because they show overall superior performance in charging the particles.
The weight ratio of the ionic dispersants to the nonionic surfactants used in step (i) is preferably from 10/90 to 40/60 in the superheavy oil emulsion fuel obtained in step (ii).
The amount of the ionic dispersants in the present invention are so adjusted that the amount thereof makes up from 0.01 to 0.5% by weight, preferably 0.02 to 0.2% by weight of the emulsion fuel obtained in step (ii). The ionic dispersant may be added as it is, or as an aqueous solution.
In addition, cationic surfactants, nonionic surfactants, thickening agents, and the stabilizers, namely polymeric compounds or water-swellable clay minerals usable in step (i), may be added as long as added in an amount expressed by weight ratio to the anionic dispersants, is preferably within the range of from 1/100 to 1/5.
In step (ii), the agitation while adding to and blending at least one of water and ionic dispersants with the emulsion fuel obtained in step (i) is carried out with a generally employed agitator, such as propeller CA 0220~294 1997-0~-14 agitators. In step (ii), subsequent to the preparation of the liquid mixture, the resulting liquid mixture is agitated with a sheer rate of from 10/sec to 10000/sec, preferably from 100/sec to 6000/sec. The shear rate is preferably 10000/sec or less from the viewpoint of significantly reducing the effects to the oil droplet particles of the emulsion fuel obtained in step (ii), thereby making it possible to maintain good long-term storage stability of the resulting emulsion fuel.
10The resulting emulsion fuel obtained in step (ii) comprising the oil-in-water (0/W) droplets has a superheavy oil concentration of from 68 to 79% by weight, preferably from 75 to 79% by weight, and a viscosity at 25~C is preferably from 200 to 1500 c.p., more preferably 15from 300 to 600 c.p. When optionally using water, the concentration of the superheavy oil in the emulsion fuel obtainable in step (ii) is lowered from that in the emulsion fuel obtainable in step (i) preferably by 1 to 6%
by weight. Also, the emulsion fuel obtained in step (ii) comprises the oil-in-water (0/W) droplets having a particle size distribution of which a 50%-cumulative particle size is preferably from 8 to 30 ,um, more preferably from 10 to 20 ,um, still more preferably from 12 to 16 ,um, and coarse particles having particle sizes of 150 ,um or more occupy preferably 3% by weight or less, CA 0220~294 1997-0~-14 more preferably 2~ by weight or less, still more preferably 1~ by weight or less, in the entire oil droplets, which is usable as fuels for thermoelectric power generation.
The superheavy oil emulsion fuel obtainable by the method of the present invention having a high superheavy oil concentration has a small amount of coarse particles and good flowability, and also has good long-term storage stability, so that its handling is made easy, thereby making it highly valuable when used as fuels.
EXAMPLES
The present invention will be explained in detail by means of the following working examples, without intending to restrict the scope of the present invention thereto.
Example 1 A 800 ml-stainless steel container was charged with given amounts of water and asphalt ("STRAIGHT ASPHALT,"
according to JIS K-2207, manufactured by Cosmo Oil Co.;
penetration: 80 to 100), and at least one of surfactants and stabilizers shown in Tables 1 to 6, and the ingredients were heated to a given temperature of 80~C in a thermostat. Thereafter, the mixture in the container was mixed in advance using an agitator equipped with CA 0220~294 1997-0~-14 double, helical ribbon blades for 5 minutes at a rotational speed of 60 r.p.m., and then the resulting mixture was blended and emulsified using a "T.K. HOMO
MIXER, Model M" (equipped with low-viscosity agitating blades; manufactured by Tokushu Kika Kogyo) to produce an emulsion fuel under the following conditions. Here, the emulsion fuel prepared above is referred to as "concentrated (conc.) emulsion," and this step is referred to as "Step (i)."
The agitation conditions are as follows.
Agitation rotational speed: 8000 r.p.m.
Agitation time: 2 minutes.
Temperature: 80~C.
Shear rate: 12000/sec.
Here, the specific gravity of water is 0.997 (25~C), and the specific gravity of oil is 1.026 (25~C). The viscosity is measured by using a double, cylindrical rotational viscometer "RV-2" (equipped with a sensor "MV-1," manufactured by Haake Co.) at 25~C while applying a shearing rate of 100/sec.
The particle size of the oil droplets of the obtained emulsion fuel is evaluated by using a granulometer "HR850-B" (manufactured by Cyrus Co.) to determine 50%-cumulative particle size (average particle diameter).
CA 0220~294 1997-0~-14 Specifically, the particle size is evaluated by the following method. Several droplets of the emulsion fuel are added in an aqueous solution containing 0.3% by weight of a nonionic surfactant (polyoxyethylene(20 mol) nonyl phenyl ether), and the resulting mixture is agitated using a stirrer, to provide a homogeneous liquid mixture. The homogeneous liquid mixture obtained above is placed in a granulometer to evaluate granularity. The measurement mode is set at 1 to 600 ,um.
The amount of coarse particles is evaluated by measuring the components having particle sizes of 150 ,um or more using a wet sieve. Specifically, 20 g of each the emulsion fuels is weighed and then poured on the sieve.
After rinsing the mesh-on particles with water, they are dried with a vacuum dryer. The amount of the particles remaining on the sieve after drying is measured to calculate the amount of coarse particles.
Next, given amounts of water heated at 80~C and an ionic dispersant listed in Table 1 to 6 were added to the concentrated emulsion prepared above. The mixture in the container was mixed in advance using an agitator equipped with double, helical ribbon blades for 5 minutes at a rotational speed of 60 r.p.m. Thereafter, the resulting mixture was blended and emulsified using a "T.K. HOMO
MIXER, Model M" (manufactured by Tokushu Kika Kogyo) to CA 0220~294 1997-0~-14 produce a desired emulsion fuel under the following conditions. Here, this step is referred to as "Step ( ii ) . "
The agitation conditions are as follows:
Agitation rotational speed: 3000 r.p.m.
Agitation time: 2 minutes.
Temperature: 80~C.
Shear rate: 4500/sec.
Inventive Sample Nos. 1 to 29 thus prepared are shown in Table 1 to 6. Here, except for Inventive Sample No. 29 where it was prepared by a method which was different from method of preparing the remaining Inventive Samples in that Step (ii) was carried out at 25~C, and Inventive Samples were all prepared under the same conditions. The average particle diameter immediately after the preparation and the amount of coarse particles were measured in the same manner as above.
Also, the obtained emulsion fuel is stored for a long term (three months), and emulsion stability after three month is evaluated by the amount of sediments, and the emulsion stability is determined by the following standards:
o: Very excellent;
c: Good;
~: Slight effect; and x: No effects.
In the tables, carboxymethylcellulose is abbreviated as "CMC."
CA 0220~294 1997-0~-14 Tab 1 e Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) (~ m) (wt%) Polyoxyethylene nonylphenyl ether l(HLB 15.5) 0.30wt% 2800 77 15.3 0.5 C M C 0.02wt%
Polyoxyethylene nonylphenyl ether 2(HLB 15.5) 0.30 wt% 2900 78 14.8 0.4 C M C O . 005wt%
Polyoxyethylene nonylphenyl ether 3(HLB 15.5) 0.30 wt% 2000 78 14.1 0.7 C M C 0.003wt%
Polyoxyethylene nonylphenyl ether 2500 75 13.0 0.3 4(HLB 15.5) 0.30wt%
C M C 0.10wt%
Polyoxyethylene nonylphenyl ether 2800 75 15.3 0.5 5(HLB 15.5) 0.30wt%
C M C 0.02wt%
CA 0220~294 1997-0~-14 Tab 1 e 1 (Cont i nued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp)(wt%) (~ m) (wt%) Mons.) Formalin Condensate of Sodium Naphtha-1 lenesulfonate 340 75 15.2 1.5 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-2 lenesulfonate 270 75 14.7 0.4 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-3 lenesulfonate 250 75 14.9 0.8 0 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-4 lenesulfonate 390 74 12.7 0.3 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-lenesulfonate 350 75 15.3 0.4 (Degree of Conden-sation: 10.2) 0.02wt%
CA 0220~294 1997-0~-14 Tab 1 e 2 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) ( ~ m ) (wt%) Polyoxyethylene nonylphenyl ether 6(HLB 15.5) 0.30wt% 2800 75 15.3 0.5 C M C O . 02wt%
Polyoxyethylene nonylphenyl ether 7(HLB 15.5) 0.30wt% 2800 77 15.3 0.5 C M C O . 02wt%
Polyoxyethylene nonylphenyl ether 8(HLB 15.5) 0.30wt% 2800 77 15.3 0.5 Xanthan gum 0.02wt%
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
9 2100 77 15.4 0.7 Polyvinylpyrrolidone (Molecular weight:
100000) 0.02wt%
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
2200 77 15.5 0.8 Polyvinyl Alcohol (Molecular weight:
100000) 0.02wt~
CA 0220~294 1997-0~-14 Tab 1 e 2 (Cont inued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt%) Mons.) Formalin Condensate of Sodium Naphtha-6 lenesulfonate 320 75 15.5 0.7 (Degree of Conden-sation: 10.2) 0.10wt~
Formalin Condensate of Sodium Naphtha-7 lenesulfonate 290 75 16.2 1.1 0 (Degree of Conden-sation: 10.2) 0.20wt%
Formalin Condensate of Sodium Naphtha-8 lenesulfonate 350 75 15.2 0.6 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-9 lenesulfonate 300 75 15.3 0.8 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-lenesulfonate 310 75 15.6 0.8 (Degree of Conden-sation: 10.2) 0.05wt%
CA 0220~294 1997-0~-14 Table 3 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt~) Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
11 2000 77 15.5 0.9 Polyvinylacrylamide (Molecular weight:
100000) 0.02wt~
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt~
1900 77 15.7 1.0 12Montmorilonite (Average Particle Size: 1.5 ~ m ) 0.05wt~
Polyoxyethylene nonylphenyl ether 13(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C O . 02wt%
Polyoxyethylene nonylphenyl ether 14(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 15(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
CA 0220~294 1997-0~-14 Tab 1 e 3 (Con t i nu e d) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate of Sodium Naphtha-11 lenesulfonate 300 75 15.7 1.O
(Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-12 lenesulfonate 280 75 15.8 1.1 (Degree of Conden-sation: 10.2) 0.05wt%
Sodium lignin-13 sulfonate 350 75 15.2 0.5 0.05wt~
Sodium polystyrene-14 sulfonate 370 75 15.2 0.6 0.05wt~
Sodium dodecyl benzenesulfonate 330 75 15.3 0.5 0.05wt%
CA 0220~294 1997-0~-14 Tab 1 e 4 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) ( ~ m) (wt~) Polyoxyethylene nonylphenyl ether 16(HLB 15.5) 0.40wt~ 2800 77 12.0 0.4 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 17(HLB 15.5) 0.80wt~ 3500 77 8.0 0.3 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 18(HLB 15.5) 0.20wt~ 2900 77 18.2 2.6 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 19(HLB 15.5) 0.10wt~ 3700 77 19.4 5.8 C M C o . 02wt~
Polyoxyethylene nonylphenyl ether 20(HLB 15.5) 0.30wt~ 2800 77 15.0 0.6 C M C 0.02wt~
CA 0220~294 1997-0~-14 T a b 1 e 4 ( C o n t i n u e d ) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate of Sodium Naphtha-16 lenesulfonate 350 75 12.2 0.4 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-17 lenesulfonate 950 75 8.0 0.3 A
(Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-18 lenesulfonate 550 75 18.4 2.6 O
(Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-19 lenesulfonate 720 75 19.5 5.9 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-lenesulfonate 360 75 15.1 0.6 (Degree of Conden-sation: 10.2) 0.05wt~
CA 0220~294 1997-0~-14 Tab 1 e 5 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt%) Polyoxyethylene dodecylphenyl ether 21(HLB 15.5) 0.30wt~ 2700 77 14.9 0.5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 22(HLB 15.5) 0.30wt~ 2600 77 16.6 2.0 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 23(HLB 15.5) 0.30wt~ 2700 77 15.8 0.9 C M C 0.02wt~
Polyoxyethylene oleyl ether 24(HLB 15.5) 0.30wt~ 2200 77 19.5 4.8 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 25(HLB 15.5) 0.30wt~ 2200 76 15.5 0.6 C M C 0.05wt~
CA 0220~294 1997-0~-14 Tabl e 5 (Cont inued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate of Sodium Naphtha-21 lenesulfonate 340 75 15.0 0.6 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-22 lenesulfonate 290 75 16.7 2.1 0 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-23 lenesulfonate 330 75 15.7 1.0 (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-24 lenesulfonate 280 75 13.5 4.9 0 (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-lenesulfonate 180 70 15.6 0.5 (Degree of Conden-sation: 10.2) 0.05wt~
CA 0220~294 1997-0~-14 T a b l e 6 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt~) Polyoxyethylene nonylphenyl ether 26(HLB 15.5) 0.30wt~ 2300 79 16.2 1.3 C M C O . 05wt~
Polyoxyethylene nonylphenyl ether 27(HLB 15.5) 0.30wt~ 2900 81 18.4 2.0 C M C O . 05wt~
Polyoxyethylene nonylphenyl ether 28(HLB 15.5) 0.30wt~ 890 79 15.4 1.3 CMC O wt~
Polyoxyethylene nonylphenyl ether 29(HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
CA 0220~294 1997-0~-14 Tab 1 e 6 (Cont i nued) Step (ii) Desired Emulsion Product Inventive Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp)(wt%) (J' m) (wt%) Mons ) Formalin Condensate of Sodium Naphtha-980 78 16.2 1.3 26 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate of Sodium Naphtha-270 75 18.5 2.1 27 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-210 75 15.3 2.8 28 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt%
Formalin Condensate of Sodium Naphtha-390 75 15.3 1.7 29 lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt%
CA 0220~294 1997-0~-14 Example 2 Step (i) was carried out in the same manner as in Example 1, to give concentrated emulsion. In step (ii), water and an ionic dispersant were added to the resultant emulsion. The mixture was agitated in the same manner as in Example 1, and then the resulting mixture was blended and emulsified using a "T.K. HOMO MIXER, Model M"
(manufactured by Tokushu Kika Kogyo) to produce an emulsion fuel under the agitation conditions given in Tables 7 and 8.
The resulting emulsion fuel was evaluated in the same manner as in Example l, and the physical properties are also shown in Tables 7 and 8. Inventive Sample Nos. 30 to 35 are cases where an ionic dispersant and water are added; Inventive Sample Nos 36 to 39 are cases where only concentrated aqueous solution of at least one ionic dispersant is added without adding optional water in step (ii) .
Also, in order to maintain viscosity in step (i), the procedures of step (ii) were carried out at 80~C. As for Inventive Samples 36 to 39 of Table 8, the viscosity of step (i) was measured at 80~C.
CA 0220~294 1997-0~-14 Tabl e 7 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m) (wt%) Polyoxyethylene nonylphenyl ether 30( HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 31( HLB 15 . 5 ) O . 30wt~ 2800 77 15 . 3 0. 5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 32( HLB 15 . 5 ) O . 30wt% 2800 77 15 . 3 O. 5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 33( HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C O . 02wt~
Polyoxyethylene nonylphenyl ether 34( HLB 15.5) 0.30wt~ 2800 77 15.3 0.5 C M C 0.02wt~
Tab 1 e 7 (Cont inued) Step (ii) Desired Emulsion Product Shear Inventive Ionic C,ondi-Conc. of Sta-Sample Di~ ,tstions Visco- Super- Average C,oarse bility Nos. of Step sity heavy Particle Parti- (After (ii) Oil Size cles Three (cp)(wt%) (J~ m) (wt%) Mons.) Formalin Crn~nqate of Sodium Naphtha-lenesulfonate 1200/s 420 75 15.2 0.6 (Degree of Conden-sation: 10.2) 2 min.
0.075wt~
Formalin C~n~Pnq~te of Sodium Naphtha-31 lenesulfonate 600/s 900 75 15.3 0.6 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
Formalin C,ondensate of Sodium Naphtha-32 lenesulfonate 3000/s 350 75 15.2 0.6 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
Formalin Cm ~nqate of Sodium Naphtha-33 lenesulfonate 6000/s 340 75 15.1 0.7 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
Formalin Condensate of Sodium Naphtha-34 lenesulfonate 12000/s 320 75 15.6 1.5 (Degree of C,onden-sation: 10.2) 2 min.
0.075wt%
CA 0220~294 1997-0~-14 Tabl e 8 Step (i) Thick Emulsion Fuel InventiveSurfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp)(wt%) ( ~ m) (wt%) Polyoxyethylene nonylphenyl ether 35(HLB 15.0) 0.40wt~ 1500 78 15.2 0.3 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 36(HLB 15.0) 0.40wt~ 1500 78 15.2 0.3 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 37(HLB 15.0) 0.40wt% 1900 79 15.8 0.4 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 38(HLB 15.0) 0.40wt~ 2200 80 17.5 1.4 CMC 0.01wt%
Polyoxyethylene nonylphenyl ether 39(HLB 15.0) 0.40wt% 2200 80 17.5 1.4 C M C 0.01wt%
T a b 1 e 8 (C o n t i n u e d) Step (ii) Desired Emulsion Product Shear Inventive Ionic Condi-Conc. of Sta-Sample Dispersants tions Visco- Super- Average Ccarse bility Nos. of Step sity heavy Particle Parti- (After (ii) Oil Size cles Three (cp)(wtO (~ m) (wt O Mons.) Sodium lignin-35sulfonate 1200/9 631 77 15.2 0.7 0.075wt~ 2 min.
Sodium lignin-36sulfonate 1200/s 433 77 15.3 0.3 0.10 wt~ 2 min.
Sodium lignin-37sulfonate 1200/s 620 78 15.2 0.5 0.15 wt% 2 min.
Sodium lignin-38sulfonate 1200/s 840 79 17.4 1.4 0.20 wt~ 2 min.
Sodium lignin-sulfonate 390.20 wt~ 1200/s 950 79 17.6 1.5 CMC 0.0C5wt~ 2 min.
CA 0220~294 1997-0~-14 Comparative Example The same procedures as in Example 1 were carried using at least one of surfactants and stabilizers shown in Table 9, to give Comparative Samples 1 to 4.
The physical properties are evaluated in the same manner as in Example 1, and the results are also shown in Table 9. The physical properties of Comparative Sample No. 3 could not be evaluated, because no emulsion was formed in this sample.
CA 0220~294 1997-0~-14 Tab 1 e 9 Step (i) Thick Emulsion Fuel Comparative Surfactants Conc. of Sample and Visco- Super- Average Coarse Nos. Stabilizers sity heavy Particle Parti-Oil Size cles (cp) (wt~ m ) (wt~) Polyoxyethylene nonylphenyl ether 1(HLB 12.5) 0.30wt% > 3500 77 18.5 7.5 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 2(HLB 19.3) 0.30wt~ > 3500 79 20.4 6.6 C M C 0.02wt~
Polyoxyethylene nonylphenyl ether 3(HLB 15.5) 0.05wt~
C M C 0.02wt~
Polyoxyethylene nonylphenyl ether (HLB 15.5) 0.30wt%
C M C O . 02wt~
4Formalin Condensate 290 75 16.1 6.1 of Sodium Naphtha-lenesulfonate (Degree of Conden-sation: 10.2) 0.075wt~
CA 0220~294 1997-0~-14 Tab 1 e 9 (Cont inued) Step (ii) Desired Emulsion Product Comparative Ionic Conc. of Sta-Sample Dispersants Visco- Super- Average Coarse bility Nos. sity heavy Particle Parti- (After Oil Size cles Three (cp) (wt~ m) (wt~) Mons.) Formalin Condensate l of Sodium Naphtha- > 3500 75 18.5 7.5 X
lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt~
Formalin Condensate 2 of Sodium Naphtha- >3500 75 21.0 6.8 X
lenesulfonate (Degree of Conden-sation: 10.2) 0.05wt~
CA 0220~294 1997-0~-14 -- 70 -- .
As is clear from Tables 1 to 10, when compared with the comparative samples, all of the emulsion fuels of the inventive samples prepared according to the method of the present invention have smaller amount of coarse particles and excellent flowability and long-term storage ability.
The present invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.
Claims (13)
1. A method for producing a superheavy oil emulsion fuel comprising the steps of:
(i) preparing a liquid mixture comprising a superheavy oil, water, one or more nonionic surfactants having an HLB ( hydrophilic-lipophilic balance) of 13 to 19, and optionally one or more stabilizers, and then agitating the resulting liquid mixture with a high shear rate of 1000/sec to 60000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 74 to 82%
by weight, wherein said nonionic surfactants are contained in an amount of from 0.1 to 0.8% by weight of the emulsion fuel obtained in step (i), and wherein said stabilizers, when added, are contained in an amount of from 0.001 to 0.5%
by weight of the emulsion fuel obtained in step (i); and (ii) adding at least one of ionic dispersants, and optionally water, to the emulsion fuel obtained in step (i), and then blending and agitating the resulting liquid mixture with a shear rate of 10/sec to 10000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 68 to 79% by weight, wherein said ionic dispersants are contained in an amount of from 0.01 to 0.5% by weight of the emulsion fuel obtained in step (ii).
(i) preparing a liquid mixture comprising a superheavy oil, water, one or more nonionic surfactants having an HLB ( hydrophilic-lipophilic balance) of 13 to 19, and optionally one or more stabilizers, and then agitating the resulting liquid mixture with a high shear rate of 1000/sec to 60000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 74 to 82%
by weight, wherein said nonionic surfactants are contained in an amount of from 0.1 to 0.8% by weight of the emulsion fuel obtained in step (i), and wherein said stabilizers, when added, are contained in an amount of from 0.001 to 0.5%
by weight of the emulsion fuel obtained in step (i); and (ii) adding at least one of ionic dispersants, and optionally water, to the emulsion fuel obtained in step (i), and then blending and agitating the resulting liquid mixture with a shear rate of 10/sec to 10000/sec, to give an oil-in-water (O/W) type emulsion fuel having a superheavy oil concentration of from 68 to 79% by weight, wherein said ionic dispersants are contained in an amount of from 0.01 to 0.5% by weight of the emulsion fuel obtained in step (ii).
2. The method according to claim 1, wherein at least one of anionic surfactants and cationic surfactants is further added in the preparation of the liquid mixture in step (i), the weight ratio of at least one of anionic surfactants and cationic surfactants to the nonionic surfactants being from 1/100 to 1/4.
3. The method according to claim 1 or 2, wherein said stabilizers are at least one member selected from polymeric compounds and water-swellable clay minerals.
4. The method according to any one of claims 1 to 3, wherein said oil-in-water (O/W) type emulsion fuel in step (i) has a superheavy oil concentration of from 77 to 81% by weight.
5. The method according to any one of claims 1 to 4, wherein in the preparation of the liquid mixture in step (i), said nonionic surfactants are contained in an amount of from 0.2 to 0.4% by weight of the emulsion fuel obtained in step (i), and said stabilizers are contained in an amount of from 0.005 to 0.1% by weight of the emulsion fuel obtained in step (i); and wherein in step (ii), said dispersants are contained in an amount of from 0.02 to 0.2% by weight of the emulsion fuel obtained in step (ii).
6. The method according to any one of claims 1 to 5, wherein the weight ratio of said nonionic surfactants to said ionic dispersants, namely nonionic surfactants/ionic dispersants, is from 90/10 to 60/40 in the superheavy oil emulsion fuel obtained in step (ii).
7. The method according to any one of claims 1 to 6, wherein the liquid mixture in step (i) is agitated with a shear rate of from 5000/sec to 20000/sec, and wherein the liquid mixture in step (ii) is agitated with a shear rate of from 100/sec to 6000/sec.
8. The method according to any one of claims 1 to 7, wherein said oil-in-water (O/W) type emulsion fuel obtained in step (i) comprises oil droplets having a particle size distribution of which a 50%-cumulative particle size is from 3 to 30 µm, and coarse particles having particle sizes of 150 µm or more occupy 3% by weight or less in the entire oil droplets.
9. The method according to any one of claims 1 to 8, wherein said oil-in-water (O/W) type emulsion fuel obtained in step (i) has a viscosity at 25°C of from 400 to 3000 c.p.
10. The method according to any one of claims 1 to 9, wherein a homomixer equipped with a high-shear turbine mixer is used in step (i) as an agitator with a high shear rate.
11. The method according to any one of claims 1 to 10, wherein said oil-in-water (O/W) type emulsion fuel obtained in step (i) comprises oil droplets of which coarse particles having particle sizes of 150 µm or more occupy 2% by weight or less in the entire oil droplets.
12. The method according to any one of claims 1 to 11, wherein in the preparation of the liquid mixture in step (i), at least one member selected from magnesium acetate, magnesium sulfate, magnesium nitrate, calcium acetate, calcium sulfate, calcium nitrate, iron acetate, iron sulfate, and iron nitrate is further added to said liquid mixture, in an amount of from 0.01 to 0.2% by weight of the emulsion fuel obtained in step (i).
13. A superheavy oil emulsion fuel obtainable by the method according to any one of claims 1 to 12.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP8-153184 | 1996-05-23 | ||
JP15318496 | 1996-05-23 |
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CA2205294A1 true CA2205294A1 (en) | 1997-11-23 |
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CA002205294A Abandoned CA2205294A1 (en) | 1996-05-23 | 1997-05-14 | Method for producing superheavy oil emulsion fuel and fuel produced thereby |
Country Status (8)
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US (1) | US5851245A (en) |
EP (1) | EP0808889B1 (en) |
KR (1) | KR100305228B1 (en) |
CA (1) | CA2205294A1 (en) |
DE (1) | DE69708502D1 (en) |
MX (1) | MX9703829A (en) |
MY (1) | MY132623A (en) |
TW (1) | TW410231B (en) |
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EP1111027B1 (en) * | 1998-07-03 | 2009-06-17 | Shimada, Tadanao | Water-in-oil type emulsion fuel oil |
US6368367B1 (en) | 1999-07-07 | 2002-04-09 | The Lubrizol Corporation | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition |
US6383237B1 (en) | 1999-07-07 | 2002-05-07 | Deborah A. Langer | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel compositions |
US6368366B1 (en) | 1999-07-07 | 2002-04-09 | The Lubrizol Corporation | Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition |
US20040111956A1 (en) * | 1999-07-07 | 2004-06-17 | Westfall David L. | Continuous process for making an aqueous hydrocarbon fuel emulsion |
US6530964B2 (en) | 1999-07-07 | 2003-03-11 | The Lubrizol Corporation | Continuous process for making an aqueous hydrocarbon fuel |
US6652607B2 (en) | 1999-07-07 | 2003-11-25 | The Lubrizol Corporation | Concentrated emulsion for making an aqueous hydrocarbon fuel |
US6913630B2 (en) | 1999-07-07 | 2005-07-05 | The Lubrizol Corporation | Amino alkylphenol emulsifiers for an aqueous hydrocarbon fuel |
US6827749B2 (en) | 1999-07-07 | 2004-12-07 | The Lubrizol Corporation | Continuous process for making an aqueous hydrocarbon fuel emulsions |
US6419714B2 (en) | 1999-07-07 | 2002-07-16 | The Lubrizol Corporation | Emulsifier for an acqueous hydrocarbon fuel |
JP2002038169A (en) * | 2000-05-19 | 2002-02-06 | Taiho Ind Co Ltd | Fuel additive for bitumen heavy oil o/w emulsion fuel |
AU2002246715B2 (en) * | 2000-12-29 | 2007-10-18 | Ge Betz, Inc. | Stabilizer blends for alcohol in hydrocarbon fuel |
US7344570B2 (en) | 2001-08-24 | 2008-03-18 | Clean Fuels Technology, Inc. | Method for manufacturing an emulsified fuel |
US7413583B2 (en) | 2003-08-22 | 2008-08-19 | The Lubrizol Corporation | Emulsified fuels and engine oil synergy |
KR100743030B1 (en) * | 2005-10-06 | 2007-07-26 | 엔바로테크 주식회사 | Clean Oil including Water homogeneous-dispersely mixed therewith and Method thereof |
US20110265370A1 (en) * | 2005-11-14 | 2011-11-03 | German Avila | Three phase emulsified fuel and method of preparation and use |
ATE491861T1 (en) | 2006-02-07 | 2011-01-15 | Diamond Qc Technologies Inc | FLUE GAS INJECTION ENRICHED WITH CARBON DIOXIDE FOR HYDROCARBON EXTRACTION |
JP4382112B2 (en) * | 2007-05-24 | 2009-12-09 | Sriスポーツ株式会社 | Golf ball and manufacturing method thereof |
JP5139099B2 (en) * | 2008-01-31 | 2013-02-06 | 英介 山田 | Golf ball |
JP5331544B2 (en) * | 2008-04-21 | 2013-10-30 | ダンロップスポーツ株式会社 | Golf ball |
JP5305718B2 (en) * | 2008-04-21 | 2013-10-02 | ダンロップスポーツ株式会社 | Golf ball |
JP4964921B2 (en) * | 2009-06-29 | 2012-07-04 | Sriスポーツ株式会社 | Golf ball |
KR101228545B1 (en) * | 2010-04-14 | 2013-01-31 | 한국과학기술연구원 | A Catalyst Slurry Composition, a Method for Preparing a Membrane-Electrode Assembly For Fuel Cell Using the Same and the Membrane-Electrode Assembly For Fuel Cell Prepared Therefrom |
WO2015150971A1 (en) * | 2014-04-03 | 2015-10-08 | Fuber Limited | Emulsifying additive for forming emulsions of water in heavy fuel oil (hfo) |
WO2016074903A1 (en) | 2014-11-10 | 2016-05-19 | Eme International Limited | Device for mixing water and diesel oil, apparatus and process for producing a water/diesel oil micro-emulsion. |
WO2016101113A1 (en) * | 2014-12-23 | 2016-06-30 | Rhodia Operations | Slurry suspension comprising torrefied wood particles |
CA3004195C (en) * | 2015-11-06 | 2023-05-09 | Quadrise International Ltd | Oil-in-water emulsions |
IT201600132801A1 (en) | 2016-12-30 | 2018-06-30 | Eme International Ltd | Apparatus and process for producing liquid from biomass, biofuel and biomaterial |
US11434443B2 (en) * | 2020-04-27 | 2022-09-06 | Hindustan Petroleum Corporation Limited | Water-hydrocarbon fuel emulsion |
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US5603864A (en) * | 1991-12-02 | 1997-02-18 | Intevep, S.A. | Method for the preparation of viscous hydrocarbon in aqueous buffer solution emulsions |
US5551956A (en) * | 1992-08-05 | 1996-09-03 | Kao Corporation | Superheavy oil emulsion fuel and method for generating deteriorated oil-in-water superheavy oil emulsion fuel |
US5411558A (en) * | 1992-09-08 | 1995-05-02 | Kao Corporation | Heavy oil emulsion fuel and process for production thereof |
JPH06145677A (en) * | 1992-10-30 | 1994-05-27 | Kao Corp | Super heavy oil emulsion fuel |
JPH06322382A (en) * | 1993-03-17 | 1994-11-22 | Kao Corp | Residual oil emulsion fuel composition |
EP0732144B1 (en) * | 1995-03-17 | 1998-06-10 | Intevep SA | An emulsion formation system and mixing device |
JPH08325582A (en) * | 1995-06-01 | 1996-12-10 | Kao Corp | Production of superheavy oil emulsion fuel |
-
1997
- 1997-05-14 CA CA002205294A patent/CA2205294A1/en not_active Abandoned
- 1997-05-16 TW TW086106511A patent/TW410231B/en not_active IP Right Cessation
- 1997-05-21 EP EP97108213A patent/EP0808889B1/en not_active Expired - Lifetime
- 1997-05-21 DE DE69708502T patent/DE69708502D1/en not_active Expired - Lifetime
- 1997-05-22 MY MYPI97002218A patent/MY132623A/en unknown
- 1997-05-23 US US08/863,017 patent/US5851245A/en not_active Expired - Fee Related
- 1997-05-23 MX MX9703829A patent/MX9703829A/en not_active IP Right Cessation
- 1997-05-23 KR KR1019970020385A patent/KR100305228B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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MX9703829A (en) | 1998-04-30 |
DE69708502D1 (en) | 2002-01-10 |
EP0808889A3 (en) | 1998-03-18 |
EP0808889B1 (en) | 2001-11-28 |
EP0808889A2 (en) | 1997-11-26 |
TW410231B (en) | 2000-11-01 |
KR100305228B1 (en) | 2001-11-22 |
MY132623A (en) | 2007-10-31 |
US5851245A (en) | 1998-12-22 |
KR970074908A (en) | 1997-12-10 |
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